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The Effect of Supercritical Fluids on Solid Acid Catalyst Alkylation  

SciTech Connect

The alkylation of isobutane with trans-2-butene was explored over six solid acid catalysts in the liquid, near-critical liquid, and supercritical regions through the addition of an inert cosolvent to the reaction feed mixture. The addition of supercritical cosolvents did not result in sustained catalytic alkylation activity. A modest improvement in product yield was obtained with the addition of methane in the modified-liquid region; however, catalyst longevity and product selectivity were decreased compared to cosolvent-free liquid conditions. This paper describes the catalyst screening and selection process, an exploration of catalyst performance with varying concentrations of methane, and an examination of the effects of seven supercritical fluids on catalyst performance. The catalysts included two zeolites, two sulfated metal oxides, and two Nafion catalysts. Three hydrocarbons, two fluorocarbons, carbon dioxide, and sulfur hexafluoride were explored as inert cosolvents added to the reaction mixture.

Ginosar, Daniel Michael; Thompson, David Neil; Burch, Kyle Coates; Zalewski, D. J.



Solid acid catalysts: Stain and shine  

NASA Astrophysics Data System (ADS)

Catalyst particles for fluid catalytic cracking are vital for the oil-refinery industry, but their activity is hard to diagnose because of their inter- and intra-particle structural inhomogeneity. With fluorescence confocal microscopy and selective staining, one can now pinpoint the catalytic activity within single catalyst particles from an industrial reactor.

Chen, Peng



Prompt gamma activation analysis of solid acid catalysts  

SciTech Connect

Zeolite molecular sieves are important catalysts due to their porous structures, which lead to the size-selective transport of chemical products and reactants. One potential application of the size-selective molecular adsorption properties of zeolites is in the purification of hydrofluorocarbons (HFCs), which are replacing ozone-destroying chlorofluorocarbons in a wide range of uses, e.g., as refrigerants. A first step in understanding adsorption of these HFC molecules by zeolites is obtaining accurate measurements of the number of adsorbate molecules per zeolite supercage. Another class of catalysts, solid superacids, is important for chemical reactions such as isomerization of hydrocarbons, conversion of methanol into hydrocarbons, and polymerization of alkenes. For example, ZrO{sub 2} and TiO{sub 2} have been observed to behave as solid superacids when small amounts of sulfate and hydrogen are incorporated on their surfaces. The acidity of these materials can exceed 104 times that of liquid H{sub 2}SO{sub 4}. One explanation for the {open_quotes}superacid{close_quotes} properties of these materials is that hydrogen ions (Bronstead acid sites) bound to surface oxygens are rendered more acidic by electron withdrawal due to nearby sulfate (SO{sub 4}{sup 2-}) groups. There is much 4 current interest in the synthesis and properties of solid super-acids because they may ultimately replace liquid acids such as H{sub 2}SO{sub 4}, HF, and AICl{sub 3} in industrially important syntheses and thereby reduce the waste streams generated. Characterization of solid acids requires measurements of the hydrogen and sulfate concentrations for correlation with the catalytic properties. We have utilized prompt gamma neutron activation analysis to characterize a number of these materials because of its unique ability to quantitatively measure hydrogen concentrations in addition to a number of other elements.

Crawford, M.K.; Corbin, D.R.; VerNooy, P.D. [DuPont, Wilmington, DE (United States)



Replacement of liquid HâSOâ and HF with solid acid catalysts: A study of mixed metal phosphates as solid acid catalysts  

Microsoft Academic Search

The primary purpose of this LDRD was to identify and optimize materials as solid acid catalysts for the replacement of environmentally hazardous liquid acids such as HâSOâ and HF which are used as catalysts in both the petroleum and chemical industries. Liquid acids have significant safety, environmental and engineering difficulties associated with their use in process chemistry. Special equipment\\/materials need

N. B. Jackson; T. M. Nenoff; S. G. Thoma; S. D. Kohler



Acid properties of solid acid catalysts characterized by solid-state 31P NMR of adsorbed phosphorous probe molecules.  


A brief review is presented on acidity characterization of solid acid catalysts by means of solid-state phosphor-31 magic-angle-spinning nuclear magnetic resonance ((31)P MAS NMR) spectroscopy using phosphor-containing molecules as probes. It is emphasized that such a simple approach using (31)P MAS NMR of adsorbed phosphorous probe molecules, namely trimethylphosphine (TMP) and trialkylphosphine oxides (R(3)PO), represents a unique technique in providing detailed qualitative and quantitative features, viz. type, strength, distribution, and concentration of acid sites in solid acid catalysts. In particular, it will be shown that when applied with a proper choice of probe molecules with varied sizes and results obtained from elemental analysis, the amounts and locations (intracrystalline vs. extracrystalline) of different types (Brønsted vs. Lewis) of acid sites may be determined. In addition, by incorporating the NMR results with that obtained from theoretical density functional theory (DFT) calculations, correlations between the (31)P chemical shifts (?(31)P) and acidic strengths of Brønsted and Lewis acid sites may also be derived, facilitating a suitable acidity scale for solid acid catalysts. PMID:21785784

Zheng, Anmin; Huang, Shing-Jong; Liu, Shang-Bin; Deng, Feng



Different solid acid catalysts influence on properties and chemical composition change of upgrading bio-oil  

Microsoft Academic Search

Several solid acid catalysts are prepared and compared in upgrading bio-oil using ethanol and acetic acid as raw materials through the catalytic esterification reaction model. The SO42?\\/SiO2–TiO2 catalyst in the optimum experimental conditions achieved higher catalytic activity. The bio-oil was stabilized by ester reaction over SO42?\\/SiO2–TiO2 catalyst in the conditioned experiment with lowered dynamic viscosity and enhanced fluidity, which was

Min Song; Zhaoping Zhong; Jiajia Dai



Functionalized carbon nanofibers as solid-acid catalysts for transesterification.  


Carbon nanofibers (CNFs) were functionalized with aryl sulfonic acid groups using in situ diazonium coupling. The use of diazonium coupling yielded an acidic carbon material, in which the introduced acidic groups are readily accessible to the triglyceride substrate. The material is an efficient catalyst for the transesterification of triolein and methanol, outperforming conventional sulfonated carbons in both stability and activity per acid site. Upon comparing CNFs with varying degrees of functionalization, a linear correlation between sulfonic acid sites and catalytic performance was found. PMID:23908100

Stellwagen, Daniel R; van der Klis, Frits; van Es, Daan S; de Jong, Krijn P; Bitter, Johannes H



n-hydrocarbons conversions over metal-modified solid acid catalysts  

NASA Astrophysics Data System (ADS)

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.

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



Conversion of biomass into 5-hydroxymethylfurfural using solid acid catalyst.  


5-Hydroxymethylfurfural (HMF) was produced from monosaccharide (fructose and glucose), polysaccharide (inulin) and the Jerusalem artichoke juice by a simple one-pot reaction including hydrolysis and dehydration using solid acid under mild condition. Hydrated niobium pentoxide (Nb(2)O(5)·nH(2)O(2)) after pretreatment showed high catalytic activities for dehydration of mono- and polysaccharide to HMF at 433 K in water-2-butanol (2:3 v/v) biphasic system, giving high HMF yield of 89% and 54% from fructose and inulin, respectively. The HMF yield was up to 74% and 65% when inulin and Jerusalem artichoke juice were hydrolyzed by exoinulinase. The solid acid made the process environment-friendly and energy-efficient to convert carbohydrates into bio-fuels and platform chemicals. PMID:21036606

Yang, Fengli; Liu, Qishun; Bai, Xuefang; Du, Yuguang



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


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

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



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

ERIC Educational Resources Information Center

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…

Seen, Andrew J.



A highly active bagasse-derived solid acid catalyst with properties suitable for production of biodiesel.  


A novel bagasse-based solid acid catalyst was successfully prepared through sulfonation of incompletely carbonized bagasse. A range of conditions for producing the catalyst were investigated, and the optimized catalyst, produced under carbonization at 648 K for 0.5 h and sulfonation at 423 K for 15 h, showed excellent catalytic activity and resulted in around 95 % yield of methyl oleate. Its activity was not only substantially greater than that of niobic acid and Amberlyst-15, but also comparable to or superior to that of catalysts made from pure starch or glucose, respectively. Additionally, the bagasse-derived catalyst could be repeatedly employed for at least eight cycles and still retained around 90 % of its original activity, exhibiting excellent operational stability. Furthermore, the catalyst efficiently converted waste cooking oils with 38.6 wt % free fatty acids into biodiesel and afforded a high yield of about 93.8 % within 12 h. These results clearly show that the bagasse-derived catalyst is economic, eco-friendly, and promising for biodiesel production from low-cost feedstocks and may find wide applications. PMID:22693163

Lou, Wen-Yong; Guo, Qiang; Chen, Wen-Jing; Zong, Min-Hua; Wu, Hong; Smith, Thomas J



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 was functionalized by contacting the biochar with fuming sulfuric acid, either by direct contact (BC-A-LS), vapour Ecological Economic Development Studies (SEEDS) Student Report Investigation of Solid Acid Catalyst


Comparison between liquid and solid acids catalysts on reducing sugars conversion from furfural residues via pretreatments.  


Liquid sulphuric acid is adopted and compared with carbon-based sulfonated solid acids (coal tar-based and active carbon-based) for furfural residues conversion into reducing sugars. The optimum hydrolysis conditions of liquid acid are at 4% of sulphuric acid, 25:1 of liquid and solid ratio, 175°C of reaction temperature and 120 min of reaction time. The reducing sugar yields are reached over 60% on liquid acid via NaOH/H2O2, NaOH/microwave and NaOH/ultrasonic pretreatments, whereas only over 30% on solid acids. The TOFs (turnover number frequency) via NaOH/H2O2 pretreatments are 0.093, 0.020 and 0.023 h(-1) for liquid sulphuric acid, coal tar-based and active carbon-based solid acids catalysts, respectively. Considering the efficiency, cost and environment factors, the liquid and solid acids have their own advantages of potential commercial application values. PMID:24976491

Lin, Keying; Ma, Baojun; Sun, Yuan; Liu, Wanyi



Butyric acid esterification kinetics over Amberlyst solid acid catalysts: the effect of alcohol carbon chain length.  


The liquid phase esterification of butyric acid with a series of linear and branched alcohols is examined. Four strong cation exchange resins, Amberlyst™ 15, Amberlyst™ 36, Amberlyst™ BD 20, and Amberlyst™ 70, were used along with para-toluenesulfonic acid as a homogeneous catalyst. The effect of increasing alcohol carbon chain length and branching on esterification rate at 60°C is presented. For all catalysts, the decrease in turnover frequency (TOF) with increasing carbon chain length of the alcohol is described in terms of steric hindrance, alcohol polarity, and hydroxyl group concentration. The kinetics of butyric acid esterification with 2-ethylhexanol using Amberlyst™ 70 catalyst is described with an activity-based, pseudo-homogeneous kinetic model that includes autocatalysis by butyric acid. PMID:23380294

Pappu, Venkata K S; Kanyi, Victor; Santhanakrishnan, Arati; Lira, Carl T; Miller, Dennis J



Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts.  


The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH(3)OH) promoted by the conventional solid acids (H-mordenite, beta-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and gamma-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH(3)OH in the reaction of 2-aminoethanol with methanol (amine/CH(3)OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 degrees C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P(2)O(5)/SiO(2) and Cs/SiO(2), respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO(2). The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation. PMID:15186176

Oku, Tomoharu; Arita, Yoshitaka; Tsuneki, Hideaki; Ikariya, Takao



Which controls the depolymerization of cellulose in ionic liquids: the solid acid catalyst or cellulose?  


Cellulose is a renewable and widely available feedstock. It is a biopolymer that is typically found in wood, straw, grass, municipal solid waste, and crop residues. Its use as raw material for biofuel production opens up the possibility of sustainable biorefinery schemes that do not compete with food supply. Tapping into this feedstock for the production of biofuels and chemicals requires--as the first-step--its depolymerization or its hydrolysis into intermediates that are more susceptible to chemical and/or biological transformations. We have shown earlier that solid acids selectively catalyze the depolymerization of cellulose solubilized in 1-butyl-3-methylimidazolium chloride (BMIMCl) at 100 degrees C. Here, we address the factors responsible for the control of this reaction. Both cellulose and solid acid catalysts have distinct and important roles in the process. Describing the depolymerization of cellulose by the equivalent number of scissions occurring in the cellulosic chains allows a direct correlation between the product yields and the extent of the polymer breakdown. The effect of the acid strength on the depolymerization of cellulose is discussed in detail. Practical aspects of the reaction, concerning the homogeneous nature of the catalysis in spite of the use of a solid acid catalyst, are thoroughly addressed. The effect of impurities present in the imidazolium-based ionic liquids on the reaction performance, the suitability of different ionic liquids as solvents, and the recyclability of Amberlyst 15DRY and BMIMCl are also presented. PMID:20155777

Rinaldi, Roberto; Meine, Niklas; vom Stein, Julia; Palkovits, Regina; Schüth, Ferdi



Zr mesoporous molecular sieves as novel solid acid catalysts in synthesizing nitrile and caprolactam.  


Zr mesoporous materials with different Si/Zr ratio were synthesized by the surfactant-templated method involving cetyl trimethyl ammonium bromide (CTAB) as template and tetraethyl ortho silicate (TEOS) as organic source of silicon. The synthesized materials were labeled as SiZrMx (where x is Si/Zr = 10, 20 and 30). The BET analysis showed bimodal distribution of pores in SiZrMx structure. An attempt was made to generate super acidity on SiZrM20 by sulfation using sulfuric acid and ammonium sulfate (wt% = 4, 8 and 12). The NH3-TPD results revealed the presence of strong acidity in sulfated Zr-MCM-41. To understand the nature of acidity in Sulfated Zr-MCM-41, the efficiency of the materials is investigated in dehydration of Oximes. The industrially important materials caprolactam and intermediate nitrile were synthesized from their oximes in liquid phase system. Due to strong acidity in sulfated Zr-MCM-41, fast deactivation was observed during the synthesis of caprolactam but, the catalyst showed 96% nitrile selectivity. The strong acidity and medium strong acidity favoured the formation of nitrile and caprolactam respectively. This study revealed the molecular sieves were effective and eco-friendly solid acid catalysts for synthesizing caprolactam and nitrile. PMID:24734693

Nedumaran, D; Pandurangan, A



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

NASA Astrophysics Data System (ADS)

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.

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



Efficient solid acid catalyst containing Lewis and Brønsted Acid sites for the production of furfurals.  


Self-assembled nanoparticulates of porous sulfonated carbonaceous TiO2 material that contain Brønsted and Lewis acidic sites were prepared by a one-pot synthesis method. The material was characterized by XRD, FTIR spectroscopy, NH3 temperature-programmed desorption, pyridine FTIR spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, N2 -sorption, atomic absorbance spectroscopy, and inductively coupled plasma optical emission spectroscopy. The carbonaceous heterogeneous catalyst (Glu-TsOH-Ti) with a Brønsted-to-Lewis acid density ratio of 1.2 and more accessible acid sites was effective to produce 5-hydroxymethylfurfural and furfural from biomass-derived mono- and disaccharides and xylose in a biphasic solvent that comprised water and biorenewable methyltetrahydrofuran. The catalyst was recycled in four consecutive cycles with a total loss of only 3?% activity. Thus, Glu-TsOH-Ti, which contains isomerization and dehydration catalytic sites and is based on a cheap and biorenewable carbon support, is a sustainable catalyst for the production of furfurals, platform chemicals for biofuels and chemicals. PMID:24807741

Mazzotta, Michael G; Gupta, Dinesh; Saha, Basudeb; Patra, Astam K; Bhaumik, Asim; Abu-Omar, Mahdi M



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

SciTech Connect

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.

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



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


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 30min reaction time. The catalytic system was applicable to initial corn stalk concentration of up to ca. 10wt.% 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

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



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.  


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

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



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)

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.

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



Solid acid catalysts from clays: preparation of mesoporous catalysts by chemical activation of metakaolin under acid conditions.  


Natural kaolin was treated at 850 or 950 degrees C in air flow to give respectively the metakaolin samples MK8 and MK9. The obtained materials were successively treated at 90 degrees C with a 1 M solution of H(2)SO(4), for various time lengths. The acid treatment of MK8 was found to give a high surface area microporous material with good catalytic properties related to the high density of acid sites, while MK9 gave an ordered mesoporous material with a low density of acid sites. The materials were characterized by several techniques, X-ray powder diffraction, thermogravimetric analysis, N(2) physisorption, scanning electron microscopy, and temperature-programmed desorption of ammonia. The 1-butene isomerization was used as test reaction to evaluate the acidity of the samples. PMID:17451736

Lenarda, M; Storaro, L; Talon, A; Moretti, E; Riello, P



Amine functionalized K10 montmorillonite: a solid acid-base catalyst for the Knoevenagel condensation reaction.  


Different amine functionalized K10 montmorillonites were hydrothermally fabricated by a simple method of treatment of the neat clay with different amine solutions and used as heterogeneous catalysts towards the Knoevenagel condensation reaction. Catalytic results show that the di-amine functionalized K10 montmorillonite exhibits high efficacy for promoting this reaction at room temperature and in the absence of a solvent. The solid catalyst was characterized using a variety of different techniques; including Fourier transform infrared spectroscopy (FT-IR), nitrogen physisorption measurements, (29)Si CP MAS NMR spectroscopy, NH3-temperature programmed desorption (NH3-TPD), X-ray powder diffraction (XRD), and field emission scanning electron microscopy (FESEM). The catalyst could be recycled and reused for several runs without any loss of inherent catalytic activity. PMID:23400041

Varadwaj, G Bishwa Bidita; Rana, Surjyakanta; Parida, K M



In situ reactive extraction of cottonseeds with methyl acetate for biodiesel production using magnetic solid acid catalysts.  


A magnetic solid acid catalyst S2O8(2)(-)/ZrO2-TiO2-Fe3O4 was prepared by coprecipitation and impregnation methods and its catalytic activity was investigated for the reactive extraction of cottonseeds with methyl acetate to produce biodiesel. The physicochemical properties of the catalyst were characterized in detail. The influences of Zr/Ti molar ratio and calcination temperature on the catalytic performance were investigated. Moreover, optimization of the reactive extraction process was performed using response surface methodology coupled with central composite design. The catalyst with a Zr/Ti molar ratio of 3/1 calcined at 550°C showed the best activity. An optimum biodiesel yield of 98.5% was obtained under the reaction temperature of 50°C, catalyst amount of 21.3wt.%, methyl acetate/seed ratio of 13.8ml/g and 10.8h of reaction time. Reuse of this catalyst indicated that it had steady catalytic activity and high recovery rate which could be a promising catalyst for biodiesel production from oilseeds. PMID:25463798

Wu, Haitang; Liu, Yanping; Zhang, Junhua; Li, Guanglu



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


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

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



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

SciTech Connect

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.

Yu Hao [School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510641 (China)], E-mail:; Jin Yuguang; Li Zhili [School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510641 (China); Peng Feng [School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510641 (China)], E-mail:; Wang Hongjuan [School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510641 (China)



Fructose dehydration to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system.  


Different acidic heterogeneous catalysts like alumina, aluminosilicate, zirconium phosphate, niobic acid, ion-exchange resin Amberlyst-15, and zeolite MOR have been studied in fructose dehydration to 5-hydroxymethylfurfural (HMF). The acidity of these materials was characterized using temperature-programmed desorption of NH? and IR spectroscopy of adsorbed pyridine. The nature and strength of acid sites was shown to play a crucial role in the selectivity towards HMF. Brønsted acid sites in the case of zeolites and ion-exchange resin led to high selectivities in the dehydration of fructose with an increase in selectivity with the addition of an organic phase. Lewis acidity in the case of phosphate and oxides resulted in the intensive production of humins from fructose at the initial stages of the process, whereas organic phase addition did not affect selectivity. PMID:22777706

Ordomsky, Vitaly V; van der Schaaf, John; Schouten, Jaap C; Nijhuis, T Alexander



Preparation of a carbon-based solid acid catalyst by sulfonating activated carbon in a chemical reduction process.  


Sulfonated (SO(3)H-bearing) activated carbon (AC-SO(3)H) was synthesized by an aryl diazonium salt reduction process. The obtained material had a SO(3)H density of 0.64 mmol·g-1 and a specific surface area of 602 m2·g-1. The catalytic properties of AC-SO(3)H were compared with that of two commercial solid acid catalysts, Nafion NR50 and Amberlyst-15. In a 10-h esterification reaction of acetic acid with ethanol, the acid conversion with AC-SO(3)H (78%) was lower than that of Amberlyst-15 (86%), which could be attributed to the fact that the SO(3)H density of the sulfonated carbon was lower than that of Amberlyst-15 (4.60 mmol·g-1). However, AC-SO(3)H exhibited comparable and even much higher catalytic activities than the commercial catalysts in the esterification of aliphatic acids with longer carbon chains such as hexanoic acid and decanoic acid, which may be due to the large specific surface area and mesoporous structures of the activated carbon. The disadvantage of AC-SO(3)H is the leaching of SO(3)H group during the reactions. PMID:20956883

Liu, Xiao-Yan; Huang, Miao; Ma, Hai-Long; Zhang, Zeng-Qiang; Gao, Jin-Ming; Zhu, Yu-Lei; Han, Xiao-Jin; Guo, Xiang-Yun



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


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

Díaz, L; Borges, M E



Study of temperature-programmed desorption of tert-butylamine to measure the surface acidity of solid catalysts  

SciTech Connect

In this paper, the technique of temperature-programmed desorption of tert-butylamine is described to measure the surface acidity of solid catalysts. The use of this base has advantages over the use of ammonia, pyridine, and n-butylamine. The desorption measurement is carried out by two methods, gas chromatography and thermogravimetry, and the advised conditions are described for both methods. Catalysts of SiO{sub 2}/Al{sub 2}O{sub 3}, bifunctionals of Ni-SiO{sub 2}/Al{sub 2}O{sub 3}, and a commercial cracking zeolite have been studied. A comparison of the desorption results with those of the other acidity measurement techniques (such as titration with n-butylamine in the liquid phase and kinetic measurement of isomerization of n-butenes as the test reaction) allows the acidity measured with tert-butylamine desorption to be classified as strong, corresponding to the active sites in most of the reactions among the hydrocarbon compounds catalyzed by acids.

Aguayo, A.T.; Arandes, J.M.; Olazar, M.; Bilbao, J. (Dept. de Ingenieria Quimica, Univ. del Pais, Vasco. Apartado 655, 48080 Bilbao (ES))



Vapor phase nitration of benzene over solid acid catalysts IV. Nitration with nitric acid (3); supported sulfuric acid catalyst with co-feeding of a trace amount of sulfuric acid  

Microsoft Academic Search

In the vapor phase nitration of benzene with diluted nitric acid, we have succeeded in keeping a high nitration activity of the supported sulfuric acid catalyst for more than 2 months by co-feeding a trace amount of sulfuric acid (H2SO4\\/HNO3=1\\/5000 (wt. ratio)). The results after 60 days on-stream over 10wt.%–H2SO4\\/SiO2 catalyst are as follows: yield of nitrobenzene (NB), 93% based

H Sato; K Nagai; H Yoshioka; Y Nagaoka



Polypyrrole based strong acid catalyst for acetalization  

NASA Astrophysics Data System (ADS)

Novel polypyrrole based acid catalyst has been synthesized through the neutralization reaction of polypyrrole and sulfuric acid. The polypyrrole based acid owned the acidity as high as 6.0 mmol/g, which was much higher than that of the traditional solid acids such as Nafion and Amberlyst-15 (0.8 mmol/g). The catalytic activities of the novel solid acid were investigated through the acetalization. The results showed that the novel solid acid held high activities for the reactions. Furthermore, the recycled activities of the catalyst indicated that the solid acid owned high stability during the catalytic process and little acid sites dropped from polypyrrole. The high acidity and stability made the novel polypyrrole based acid hold great potential for the green chemical processes.

Liang, Xuezheng; Cheng, Yuxiao; Qi, Chenze



Xanthan Sulfuric Acid: An Efficient Bio-Supported and Recyclable Solid Acid Catalyst for the Synthesis of 4,4-(Arylmethylene)bis(1 h-Pyrazol-5-ols)  

Microsoft Academic Search

A simple and efficient method has been developed for the synthesis of 4,4-(arylmethylene)bis(1H-pyrazol-5-ols) by the condensation reaction between substituted aldehydes, and 1-phenyl-3-methylpyrazol-5-one in the presence of Xanthan sulfuric acid (XSA) as a solid acid catalyst. This method is simple, cost effective, requires short reaction times, yields are excellent with high purity and the catalyst could be easily recycled.

B. Suresh Kuarm; B. Rajitha



Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions  

PubMed Central

Summary A convenient and efficient methodology for the synthesis of densely substituted pyrrole-fused isocoumarins, which employs solid-supported silica sulfuric acid (SSA) as catalyst, has been developed. When the mixture of ninhydrin adducts of acetylacetone/ethyl acetoacetate and primary amines was heated on the solid surface of SSA under solvent-free conditions, the pyrrole-fused isocoumarins were formed in good yields. This synthetic method has several advantages such as the employment of solvent-free reaction conditions without the use of any toxic reagents and metal catalysts, the ease of product isolation, the use of a recyclable catalyst, the low cost, the easy availability of the starting materials, and the excellent yields of products. PMID:24367398

Pathak, Sudipta; Debnath, Kamalesh




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...


Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts.  


Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200-250?°C without any external added pressure, conditions significantly milder than those described previously for the same conversion with better yield and selectivity. A comprehensive study of the reaction parameters has been performed, and the isolation of methacrylic acid was achieved in 50% yield. The decarboxylation procedure is also applicable to citric acid, a more widely available bio-based feedstock, and leads to the production of methacrylic acid in one pot in 41% selectivity. Aconitic acid, the intermediate compound in the pathway from citric acid to itaconic acid was also used successfully as a substrate. PMID:25045161

Le Nôtre, Jérôme; Witte-van Dijk, Susan C M; van Haveren, Jacco; Scott, Elinor L; Sanders, Johan P M



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

E-print Network

Accepted 8 March 2009 Available online 22 April 2009 Keywords: Keggin polyoxometalates 2-Butanol for dehydration and isomerization reactions and DPE values on Keggin polyoxometalates and H-BEA solids with known

Iglesia, Enrique


Supercritical/Solid Catalyst (SSC)  


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




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

NASA Astrophysics Data System (ADS)

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.

Sadanandan, Manoj; Bhaskaran, Beena



Cellulose sulfuric acid as a bio-supported and recyclable solid acid catalyst for the one-pot three-component synthesis of ?-amino nitriles  

Microsoft Academic Search

?-Amino nitriles are synthesized by a one-pot three-component condensation reaction of amines, aldehydes and trimethylsilylcyanide in the presence of a catalytic amount of cellulose sulfuric acid as a bio-supported catalyst, in excellent yields with short reaction times at ambient temperature. The reaction work-up is simple and the catalyst can be easily separated from the product and reused in subsequent reactions.

Ahmad Shaabani; Ali Maleki



Xanthan sulfuric acid: A new and efficient bio-supported solid acid catalyst for the synthesis of ?-amino nitriles by condensation of carbonyl compounds, amines, and trimethylsilylcyanide  

Microsoft Academic Search

In this work, ?-amino nitriles are synthesized by a three-component one-pot condensation reaction of aldehydes or ketones, amines and trimethylsilylcyanide in the presence of a catalytic amount of xanthan sulfuric acid as a new bio-supported catalyst, in excellent yields with short reaction times at ambient temperature. The xanthan as the base of the catalyst was produced biologically from a native

Ahmad Shaabani; Ali Maleki; Mohammad Reza Soudi; Hamid Mofakham



Cellulose sulfuric acid as a biodegradable and recoverable solid acid catalyst for one pot synthesis of substituted pyrroles under solvent-free conditions at room temperature  

Microsoft Academic Search

A new and efficient method for the preparation of N-substituted pyrroles from one-pot condensation reaction of 2,5-hexandione with amines and diamines in the presence of cellulose sulfuric acid (CSA) as a bio-supported catalyst at room temperature under solvent-free conditions is presented. This new protocol has the advantages of easy availability, stability, reusability and eco-friendly of the catalyst, high to excellent

Ali Rahmatpour



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

SciTech Connect

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.

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



Xanthan Sulfuric Acid: A New and Efficient Bio-Supported Solid Acid Catalyst for the Synthesis of 3,4-Dihydropyrimidin-2(1H)-Ones  

Microsoft Academic Search

Xanthan sulfuric acid (XSA) is employed as a recyclable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones. These syntheses were performed via a one-pot three-component condensation of aldehydes, amines, and urea\\/thiourea under Solvent-free conditions.

B. Suresh Kuarm; J. Venu Madhav; S. Vijaya Laxmi; B. Rajitha



Cellulose sulfuric acid as a bio-supported and recyclable solid acid catalyst for the one-pot synthesis of 2,4,5-triarylimidazoles under microwave irradiation  

Microsoft Academic Search

A simple, rapid, and highly efficient method has been attempted for the three-component condensation of benzil\\/benzoin, aldehydes, and ammonium acetate under microwave irradiation in the presence of a catalytic amount of bio-supported cellulose sulfuric acid under solvent-free conditions to afford the 2,4,5-triarylimidazole derivatives. The catalyst is easily prepared, inexpensive, separated simply by filtration, gives excellent yield of products with shorter

Kiran F. Shelke; Suryakant B. Sapkal; Gopal K. Kakade; Bapurao B. Shingate; Murlidhar S. Shingare



Supported 12-tungstophosphoricacid: A recoverable solid acid catalyst for liquid phase Friedel–Crafts alkylation of phenol  

Microsoft Academic Search

Friedel–Crafts alkylation reactions such as tert-butylation, iso-propylation and sec-butylation of phenol have been carried out over 12-tungstophosphoricacid supported onto neutral alumina under mild conditions by varying different parameters. The supported catalysts were characterized by various physicochemical techniques such as FT-IR, TGA, and XPS analysis. The catalyst shows significantly high conversion and selectivity towards the important products. The catalysts were efficiently

Nikunj Bhatt; Anjali Patel



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


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

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



Isobutane\\/butene alkylation on solid catalysts. Where do we stand?  

Microsoft Academic Search

Liquid-phase processes with concentrated sulfuric acid or hydrogen fluoride as catalysts are currently being used in petroleum refining for the manufacture of alkylation gasoline from isobutane and butenes. While the product, i.e., alkylate, is a most valuable gasoline component, the existing processes for its manufacture are less satisfactory. Replacement of the liquid catalysts by a solid acid is an important

J. Weitkamp; Y. Traa



Brönsted and Lewis acidity of the BF3/gamma-Al2O3 alkylation catalyst as revealed by solid-state NMR spectroscopy and DFT quantum chemical calculations.  


Multinuclear solid-state NMR techniques and DFT quantum chemical calculations were employed to investigate the detailed structure of acid sites on the BF3/gamma-Al2O3 alkylation catalyst. The NMR experiment results indicate that gaseous BF3 is able to react with the hydroxyl groups present on the surface of gamma-Al2O3, leading to the formation of new Brönsted and Lewis acid sites. The 1H/11B and 1H/27Al TRAPDOR (TRAnsfer of Population in DOuble Resonance) experiments suggest that the 3.7 ppm signal in 1H NMR spectra of the BF3/gamma-Al2O3 catalyst is due to a bridging B-OH-Al group that acts as a Brönsted acid site of the catalyst. On the other hand, a Lewis acid site on the surface of the catalysts, as revealed by 31P MAS and 31P/27Al TRAPDOR NMR of adsorbed trimethylphosphine, is associated with three-coordinate -OBF2 species. 13C NMR of adsorbed 2-13C-acetone indicates that the Brönsted acid strength of the catalyst is slightly stronger than that of zeolite HZSM-5 but still weaker than that of 100% H2SO4, which is in good agreement with theoretical prediction. In addition, DFT calculations also reveal the detailed structure of various acid sites formed on the BF3/gamma-Al2O3 catalyst and the interaction of probe molecules with these sites. PMID:16852633

Yang, Jun; Zheng, Anmin; Zhang, Mingjin; Luo, Qing; Yue, Yong; Ye, Chaohui; Lu, Xin; Deng, Feng



Solid acid catalyzed biodiesel production from waste cooking oil  

Microsoft Academic Search

Various solid acid catalysts were evaluated for the production of biodiesel from low quality oil such as waste cooking oil (WCO) containing 15wt.% free fatty acids. The zinc stearate immobilized on silica gel (ZS\\/Si) was the most effective catalyst in simultaneously catalyzing the transesterification of triglycerides and esterification of free fatty acid (FFA) present in WCO to methyl esters. The

Kathlene Jacobson; Rajesh Gopinath; Lekha Charan Meher; Ajay Kumar Dalai



Water removal by reactive stripping for a solid-acid catalyzed esterification in a monolithic reactor  

Microsoft Academic Search

Solid-acid catalysts are attractive replacements for processes using conventional homogeneous catalysts. In the esterification of an alcohol with a carboxylic acid, however, the side product water strongly inhibits the activity of a solid-acid catalyst. Since an esterification is an equilibrium limited reaction, full conversion is not possible unless one of the products is removed. A novel reactor type, utilizing a

T. A. Nijhuis; A. E. W. Beers; F. Kapteijn; J. A. Moulijn



Immobilized cell reactors in mineralization of dicarboxylic acid solid waste  

Microsoft Academic Search

Dicarboxylic acid solid waste containing phthalic acid, malic acid, quinone, saturated and unsaturated dicarboxylic esters etc., are discharged in huge quantities during the crackdown of benzene over the catalyst vanadium at temperatures greater than 500 C in a dicarboxylic acid manufacturing industry. Concern over the biological effects of these compounds underlines the necessity to treat this solid waste. The role of

Ganesh Kumar Arumugam; Swarnalatha Somasundaram; Victor Babu Kassey; Sekaran Ganesan



Acid monolayer functionalized iron oxide nanoparticle catalysts  

NASA Astrophysics Data System (ADS)

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.

Ikenberry, Myles


The effect of acid–base pairing on catalysis: An efficient acid–base functionalized catalyst for aldol condensation  

Microsoft Academic Search

Acid–base bifunctionalized heterogeneous catalysts may be capable of exhibiting reactivity not achievable with homogeneous catalysts. We investigated the effect of pKa of the acid component of mesoporous solids containing acid–base bifunctionality on their catalytic ability toward aldol condensation between 4-nitrobenzaldehyde and acetone. We found that higher levels of aldol product conversion were obtained when weaker acid components (phosphoric, carboxylic vs

Ryan K. Zeidan; Mark E. Davis



Calcined Mg–Al hydrotalcites as solid base catalysts for methanolysis of soybean oil  

Microsoft Academic Search

Methyl ester of fatty acids, derived from vegetable oils or animal fats and known as biodiesel, is a promising alternative diesel fuel regarding the limited resources of fossil fuel and the environmental concerns. In this work, an environmentally benign process for the methanolysis of soybean oil to methyl esters using calcined Mg–Al hydrotalcites as solid base catalysts in a heterogeneous

Wenlei Xie; Hong Peng; Ligong Chen



Application of solid ash based catalysts in heterogeneous catalysis  

SciTech Connect

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.

Shaobin Wang [Curtin University of Technology, Perth, WA (Australia). Department of Chemical Engineering



Solid superacids as coal liquefaction catalysts: Quarterly report, April 1988-June 1988  

SciTech Connect

Coal liquefaction is normally achieved by using high temperatures to crack covalent bonds which form linkages in the macromolecular coal structure. Acidic catalysts can crack covalent bonds at lower temperatures. This research is centered on the use of solid superacid catalysis in coal liquefaction. During this quarter, several superacids were synthesized and characterized. The catalysts were TiO/sub 2/, and Fe/sub 2/O/sub 3/, each containing SO/sub 4//sup 2/minus// ions. These oxides possessed high acidity. The amount of acidity was measured by titrating with n-butylamine and indicators of varying pk/sub a/ values. The catalysts were characterized by surface area (BET) and x-ray diffraction (XRD). 4 refs.

Tierney, J.W.; Wender, I.



Dehydration of glycerol over niobia-supported silicotungstic acid catalysts.  


Liquid-phase dehydration of glycerol to acrolein over nanosized niobia-supported silicotungstic acid catalysts was performed to investigate the effect of the silicotungstic acid loading on the catalytic performance of the catalysts. The catalysts were prepared by following an impregnation method with different HSiW loadings in the range of 10-50 wt%. The prepared catalysts were characterized by N2 physisorption, XRD, FT-IR, TPD of ammonia, and TGA. Dehydration of glycerol was conducted in an autoclave reactor under the conditions of controlled reaction temperatures under corresponding pressure. Increasing HSiW loading rapidly increased the acidity of HSiW/Nb205 catalyst and rate of glycerol conversion, but acrolein selectivity decreased due to enhanced deactivation of the catalyst by carbon deposit. Consequently, it was confirmed that catalytic activity for the dehydration of glycerol to acrolein was dependant on the acidity of catalyst and can be controlled by HSiW loading. PMID:23646735

Lee, Young Yi; Ok, Hye Jeong; Moon, Dong Ju; Kim, Jong Ho; Park, Nam Cook; Kim, Young Chul



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

E-print Network

??This thesis describes two projects: (i) syntheses and conformational studies of cyclobutane amino acids and peptidomimetics; and, (ii) parallel screening of catalysts for asymmetric aziridination.… (more)

Li, Shih-ming



Catalyst and electrode research for phosphoric acid fuel cells  

NASA Technical Reports Server (NTRS)

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.

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



Continuous-flow hydration–condensation reaction: Synthesis of ?,?-unsaturated ketones from alkynes and aldehydes by using a heterogeneous solid acid catalyst  

PubMed Central

Summary A simple, practical and efficient continuous-flow hydration–condensation protocol was developed for the synthesis of ?,?-unsaturated ketones starting from alkynes and aldehydes by employing a heterogeneous catalyst in a flow microwave. The procedure presents a straightforward and convenient access to valuable differently substituted chalcones and can be applied on multigram scale. PMID:22238547

Bootwicha, Teerawut; Baars, Hannah; Sugiono, Erli



Novel, benign, solid catalysts for the oxidation of hydrocarbons.  


The catalytic properties of two classes of solid catalysts for the oxidation of hydrocarbons in the liquid phase are discussed: (i) microporous solids, encapsulating transition metal complexes in their cavities and (ii) titanosilicate molecular sieves. Copper acetate dimers encapsulated in molecular sieves Y, MCM-22 and VPI-5 use dioxygen to regioselectively ortho-hydroxylate L-tyrosine to L-dopa, phenol to catechol and cresols to the corresponding o-dihydroxy and o-quinone compounds. Monomeric copper phthalocyanine and salen complexes entrapped in zeolite-Y oxidize methane to methanol, toluene to cresols, naphthalene to naphthols, xylene to xylenols and phenol to diphenols. Trimeric mu3-oxo-bridged Co/Mn cluster complexes, encapsulated inside Y-zeolite, oxidize para-xylene, almost quantitatively, to terephthalic acid. In almost all cases, the intrinsic catalytic activity (turnover frequency) of the metal complex is enhanced very significantly, upon encapsulation in the porous solids. Spectroscopic and electrochemical studies suggest that the geometric distortions of the complex on encapsulation change the electron density at the metal ion site and its redox behaviour, thereby influencing its catalytic activity and selectivity in oxidation reactions. Titanosilicate molecular sieves can oxidize hydrocarbons using dioxygen when loaded with transition metals like Pd, Au or Ag. The structure of surface Ti ions and the type of oxo-Ti species generated on contact with oxidants depend on several factors including the method of zeolite synthesis, zeolite structure, solvent, temperature and oxidant. Although, similar oxo-Ti species are present on all the titanosilicates, their relative concentrations vary among different structures and determine the product selectivity. PMID:15901549

Ratnasamy, Paul; Raja, Robert; Srinivas, Darbha



Characterization of the Acid Properties of Tungsten\\/Zirconia Catalysts Using Adsorption Microcalorimetry and n-Pentane Isomerization Activity  

Microsoft Academic Search

Ammonia adsorption microcalorimetry was conducted on various solid acid tungsten\\/zirconia catalysts prepared by different techniques. The calorimetric data were compared to catalytic test results using n-pentane isomerization as a measure of acid activity. The results show that (1) the co-precipitation method of making the tungsten\\/zirconia catalyst produces a greater number of acidic sites than impregnating tungsten on hydrous zirconia, resulting

J. C. Vartuli; J. G. Santiesteban; P. Traverso; N. Cardona-Martinéz; C. D. Chang; S. A. Stevenson



Liquefaction of solid carbonaceous material with catalyst recycle  


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.

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



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

NASA Astrophysics Data System (ADS)

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.

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



Production of Jatropha biodiesel fuel over sulfonic acid-based solid acids.  


Sulfonic acid-functionalized platelet SBA-15 mesoporous silica with an acid capacity of 2.44mmol H(+) g-cat(-1) (shortly termed 15SA-SBA-15-p) was one-pot synthesized by co-condensation method. When applied as solid acid catalyst in synthesis of Jatropha biodiesel fuel (BDF), the 15SA-SBA-15-p catalyst showed higher activity and resistances to water and free fatty acid (FFA) than commercial sulfonic resins of Amberlyst-15 and SAC-13. For the continuous Jatropha BDF production, a steady 75-78wt% of fatty acid methyl ester (FAME) content was obtained over 15SA-SBA-15-p catalyst at 150°C for 75h, whereas the Amberlyst-15 and SAC-13 catalysts were quickly deactivated due to the decomposition of thermally unstable framework and serious leaching of sulfonic acids. More importantly, the quality, stability and cold flow characteristic of Jatropha BDF synthesized by 15SA-SBA-15-p catalyst were better than those synthesized by Amberlyst-15 and SAC-13 catalysts, making the blending with petro-diesel an easy task. PMID:24548779

Chen, Shih-Yuan; Lao-Ubol, Supranee; Mochizuki, Takehisa; Abe, Yohko; Toba, Makoto; Yoshimura, Yuji




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 ...


Surface acidity and degree of carburization of modified silver catalysts  

SciTech Connect

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.

Pestryakov, A.N.; Belousova, V.N.; Roznina, M.I. [Tomsk Institute of Construction Engineering (Russian Federation)



Method for producing iron-based acid catalysts  

SciTech Connect

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.

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



Method for isomerizing olefins using acidic composite catalysts  

SciTech Connect

This patent describes a method for isomerizing olefins comprising the steps of contacting at least one olefin with a catalyst composite comprising a perfluorinated-polymersulfonic acid and an anion-stabilizing agent and recovering the isomerized olefins.

Farcasiu, D.



Reactivity and Characterization of Solid State Hydrodesulfurization Catalysts.  

NASA Astrophysics Data System (ADS)

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.

Lindner, James Henry



Nanoporous solids as receptacles and catalysts for unusual conversions of organic compounds  

NASA Astrophysics Data System (ADS)

Solid-state chemical principles, allied to a degree of chemical intuition, enables one to design open-structure solids on to the inner surfaces of which isolated catalytically active sites of different kinds may be placed. With such solids, which act simultaneously both as permeable catalysts and reaction vessels, a number of highly desirable chemical conversions—many of paramount importance in the context of "green" chemistry and clean technology—may be smoothly effected under environmentally benign conditions. Typical examples, illustrated here, include the selective oxidation of toluene to benzaldehyde, current methods of producing alcohols, aldehydes and acids, and the synthesis of ?-caprolactam in a by-product-free manner. Such open-structure solids, which house single-site active centres, are also readily amenable to detailed and precise structural elucidation.

Raja, Robert; Thomas, John Meurig



Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste  

PubMed Central

In this work, sawdust, a biomass waste, is converted into a magnetic porous carbonaceous (MPC) solid acid catalyst by an integrated fast pyrolysis–sulfonation process. The resultant magnetic solid acid has a porous structure with high surface area of 296.4?m2 g?1, which can be attributed to the catalytic effect of Fe. The catalytic activity and recyclability of the solid acid catalyst are evaluated during three typical acid-catalyzed reactions: esterification, dehydration, and hydrolysis. The favorable catalytic performance in all three reactions is attributed to the acid's high strength with 2.57?mmol g?1 of total acid sites. Moreover, the solid acid can be reused five times without a noticeable decrease in catalytic activity, indicating the stability of the porous carbon (PC)–sulfonic acid group structure. The findings in the present work offer effective alternatives for environmentally friendly utilization of abundant biomass waste. PMID:23939253

Liu, Wu-Jun; Tian, Ke; Jiang, Hong; Yu, Han-Qing



Enantioselective Iodolactonization of Disubstituted Olefinic Acids Using a Bifunctional Catalyst  

PubMed Central

The enantioselective iodolactonizations of a series of diversely-substituted olefinic carboxylic acids are promoted by a BINOL-derived, bifunctional catalyst. Reactions involving 5-alkyl- and 5-aryl-4(Z)-pentenoic acids and 6-alkyl- and 6-aryl-5(Z)-hexenoic acids provide the corresponding ?- and ?-lactones having stereogenic C–I bonds in excellent yields and >97:3 er. Significantly, this represents the first organocatalyst that promotes both bromo- and iodolactonization with high enantioselectivities. The potential of this catalyst to induce kinetic resolutions of racemic unsaturated acids is also demonstrated. PMID:23199100

Fang, Chao; Paull, Daniel H.; Hethcox, J. Caleb; Shugrue, Christopher R.; Martin, Stephen F.



Low acid producing solid propellants  

NASA Technical Reports Server (NTRS)

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.

Bennett, Robert R.



Ceria-based solid catalysts for organic chemistry.  


Ceria has been the subject of thorough investigations, mainly because of its use as an active component of catalytic converters for the treatment of exhaust gases. However, ceria-based catalysts have also been developed for different applications in organic chemistry. The redox and acid-base properties of ceria, either alone or in the presence of transition metals, are important parameters that allow to activate complex organic molecules and to selectively orient their transformation. Pure ceria is used in several organic reactions, such as the dehydration of alcohols, the alkylation of aromatic compounds, ketone formation, and aldolization, and in redox reactions. Ceria-supported metal catalysts allow the hydrogenation of many unsaturated compounds. They can also be used for coupling or ring-opening reactions. Cerium atoms can be added as dopants to catalytic system or impregnated onto zeolites and mesoporous catalyst materials to improve their performances. This Review demonstrates that the exceptional surface (and sometimes bulk) properties of ceria make cerium-based catalysts very effective for a broad range of organic reactions. PMID:20486156

Vivier, Laurence; Duprez, Daniel



Electrochemical catalyst recovery method  


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.

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



Electrochemical catalyst recovery method  


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.

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



Staining of fluid-catalytic-cracking catalysts: localising Brønsted acidity within a single catalyst particle.  


A time-resolved in situ micro-spectroscopic approach has been used to investigate the Brønsted acidic properties of fluid-catalytic-cracking (FCC) catalysts at the single particle level by applying the acid-catalysed styrene oligomerisation probe reaction. The reactivity of individual FCC components (zeolite, clay, alumina and silica) was monitored by UV/Vis micro-spectroscopy and showed that only clay and zeolites (Y and ZSM-5) contain Brønsted acid sites that are strong enough to catalyse the conversion of 4-fluorostyrene into carbocationic species. By applying the same approach to complete FCC catalyst particles, it has been found that the fingerprint of the zeolitic UV/Vis spectra is clearly recognisable. This almost exclusive zeolitic activity is confirmed by the fact that hardly any reactivity is observed for FCC particles that contain no zeolite. Confocal fluorescence microscopy images of FCC catalyst particles reveal inhomogeneously distributed micron-sized zeolite domains with a highly fluorescent signal upon reaction. By examining laboratory deactivated FCC catalyst particles in a statistical approach, a clear trend of decreasing fluorescence intensity, and thus Brønsted acidity, of the zeolite domains is observed with increasing severity of the deactivation method. By comparing the average fluorescence intensities obtained with two styrenes that differ in reactivity, it has been found that the Brønsted acid site strength within FCC catalyst particles containing ZSM-5 is more uniform than within those containing zeolite Y, as confirmed with temperature-programmed desorption of ammonia. PMID:22161809

Buurmans, Inge L C; Ruiz-Martínez, Javier; van Leeuwen, Sanne L; van der Beek, David; Bergwerff, Jaap A; Knowles, William V; Vogt, Eelco T C; Weckhuysen, Bert M



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.  


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

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



Perfluorinated resinsulfonic acid--a catalyst for certain organic reactions  

SciTech Connect

The purpose of this work was to examine the possibility of using, as a catalyst in certain organic reactions, the perfluorinated resinsulfonic acid F-4SK in the H form, which is an analog of the perfluorinated resinsulfonic acid Nafion-H.

Etlis, V.S.; Beshenova, E.P.; Semenova, E.A.; Shomina, F.N.; Dreiman, N.A.; Balaev, G.A.



Transesterification of crude palm kernel oil and crude coconut oil by different solid catalysts  

Microsoft Academic Search

This work reports on the preliminary results of using several acidic and basic solids, such as ZrO2, ZnO, SO42?\\/SnO2, SO42?\\/ZrO2, KNO3\\/KL zeolite and KNO3\\/ZrO2 as heterogeneous catalysts for crude palm kernel oil (PKO) and crude coconut oil (CCO) transesterification with methanol. It was found that ZnO and SO42?\\/ZrO2 exhibited the highest activity for both PKO and CCO transesterification. In the

Jaturong Jitputti; Boonyarach Kitiyanan; Pramoch Rangsunvigit; Kunchana Bunyakiat; Lalita Attanatho; Peesamai Jenvanitpanjakul



A One-Bead-One-Catalyst Approach to Aspartic Acid-Based Oxidation Catalyst Discovery  

PubMed Central

We report an approach to the high-throughput screening of asymmetric oxidation catalysts. The strategy is based on application of the one-bead-one-compound library approach, wherein each of our catalyst candidates is based on a peptide scaffold. For this purpose we rely on a recently developed catalytic cycle that employs an acid-peracid shuttle. In order to implement our approach, we developed a compatible linker and demonstrated that the library format is amenable to screening and sequencing of catalysts employing partial Edman degradation and MALDI mass spectrometry analysis. The system was applied to the discovery (and re-discovery) of catalysts for the enantioselective oxidation of a cyclohexene derivative. The system is now poised for application to unprecedented substrate classes for asymmetric oxidation reactions. PMID:21417485

Lichtor, Phillip A.; Miller, Scott J.



Lewis acid-assisted formic acid dehydrogenation using a pincer-supported iron catalyst.  


Formic acid (FA) is an attractive compound for H2 storage. Currently, the most active catalysts for FA dehydrogenation use precious metals. Here, we report a homogeneous iron catalyst that, when used with a Lewis acid (LA) co-catalyst, gives approximately 1,000,000 turnovers for FA dehydrogenation. To date, this is the highest turnover number reported for a first-row transition metal catalyst. Preliminary studies suggest that the LA assists in the decarboxylation of a key iron formate intermediate and can also be used to enhance the reverse process of CO2 hydrogenation. PMID:24999607

Bielinski, Elizabeth A; Lagaditis, Paraskevi O; Zhang, Yuanyuan; Mercado, Brandon Q; Würtele, Christian; Bernskoetter, Wesley H; Hazari, Nilay; Schneider, Sven



Organometallic catalysts for primary phosphoric acid fuel cells  

NASA Technical Reports Server (NTRS)

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.

Walsh, Fraser



Chiral salen–metal complexes as novel catalysts for the asymmetric synthesis of ?-amino acids under phase transfer catalysis conditions  

Microsoft Academic Search

Chiral salen–metal complexes have been tested as catalysts for the C-alkylation of Schiff's bases of alanine and glycine esters with alkyl bromides under phase-transfer conditions (solid sodium hydroxide, toluene, ambient temperature, 1–10mol% of the catalyst). The best catalyst, which was derived from a Cu(II) complex of (1R, 2R or 1S,2S)-[N,N?-bis(2?-hydroxybenzylidene)]-1,2-diaminocyclohexane, gave ?-amino and ?-methyl-?-amino acids with enantiomeric excesses of 70–96%.

Yuri N Belokon; Michael North; Tatiana D Churkina; Nikolai S Ikonnikov; Victor I Maleev



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

SciTech Connect

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.

Ping, E. W.; Pierson, J.; Wallace, R.; Miller, J. T.; Fuller, T. F.; Jones, C. W. (Chemical Sciences and Engineering Division); (Georgia Institute of Technology)



Phase transitions in a bed of vanadium catalyst for sulfuric acid production: experiment and modeling  

Microsoft Academic Search

Sulfur dioxide oxidation on vanadium catalysts in sulfuric acid production may cause phase transitions in the catalyst active component. These phase transitions involve crystallization of vanadium(IV), and may influence catalyst activity. In the present study, we show that reaction mixture flow through a fixed catalyst bed is accompanied by the moving front of crystal phase, which decreases SO2 conversion at

B. S. Bal’zhinimaev; N. P. Belyaeva; S. I. Reshetnikov; E. S. Yudina; A. A. Ivanov



Thermally decomposed mesoporous Nickel Iron hydrotalcite: An active solid-base catalyst for solvent-free Knoevenagel condensation.  


Thermal decomposition of co-precipitated NiFeHT materials led to the formation a mesoporous NiFeHT catalyst and we have demonstrated here its active role as solid and active catalyst for the Knoevenagel condensation reaction of various aldehydes with active methylene compounds (RCH2CN, where RCN or CO2Et). High product yields are obtained at moderate temperature under solvent-free conditions and the catalyst can be easily separated from the reaction mixture, simply by filtration and reused several times without a significant loss of its activity. Since these mesoporous metal oxides derived from the NiFe hydrotalcites, their basicity mediated abstraction of the acidic protons from the active methylene compounds was responsible for their catalytic activity under solvent-free conditions. PMID:25490562

Dumbre, Deepa K; Mozammel, Tibra; Selvakannan, Pr; Hamid, Sharifah Bee Abdul; Choudhary, Vasant R; Bhargava, Suresh K



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...


Novel Solid Base Catalysts for the Production of Biodiesel from Lipids  

E-print Network

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...

Zhao, Lina



Proton conducting membrane using a solid acid  

NASA Technical Reports Server (NTRS)

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.

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



Acid activated montmorillonite as catalysts in methyl esterification reactions of lauric acid.  


The catalytic activity of acid activated montmorillonite in the esterification of free fatty acids (FFA) is reported. Standard Montmorillonite (MMT) type STx-1 provided by the Clay Mineral Society repository was activated using phosphoric, nitric and sulphuric acids under different conditions and the resulting materials were characterized and evaluated as catalysts in the methyl esterification of lauric acid. Blank reactions carried out in the absence of any added catalyst presented conversions of 32.64, 69.79 and 79.23%, for alcohol:lauric acid molar ratios of 60:1, 12:1 and 6:1, respectively. In the presence of the untreated clay and using molar ratios of 12:1 and 6:1 with 12% of catalyst, conversions of 70.92 and 82.30% were obtained, respectively. For the acid activated clays, conversions up to 93.08% of lauric acid to methyl laurate were obtained, much higher than those observed for the thermal conversion or using untreated montmorillonite. Relative good correlations were observed between the catalytic activity and the development of acid sites and textural properties of the resulting materials. Therefore, a simple acid activation was able to improve the catalytic activity and produce clay catalysts that are environmental friendly, cost effective, noncorrosive and reusable. PMID:22975784

Zatta, Leandro; Ramos, Luiz Pereira; Wypych, Fernando



Synthesis of methyl esters from waste cooking oil using construction waste material as solid base catalyst.  


The current research investigates synthesis of methyl esters by transesterification of waste cooking oil in a heterogeneous system, using barium meliorated construction site waste marble as solid base catalyst. The pretreated catalyst was calcined at 830 °C for 4h prior to its activity test to obtained solid oxide characterized by scanning electron microscopy/energy dispersive spectroscopy, BET surface area and pore size measurement. It was found that the as prepared catalyst has large pores which contributed to its high activity in transesterification reaction. The methyl ester yield of 88% was obtained when the methanol/oil molar ratio was 9:1, reaction temperature at 65 °C, reaction time 3h and catalyst/oil mass ratio of 3.0 wt.%. The catalyst can be reused over three cycles, offer low operating conditions, reduce energy consumption and waste generation in the production of biodiesel. PMID:23186664

Balakrishnan, K; Olutoye, M A; Hameed, B H



Carbocations as Lewis acid catalysts in Diels-Alder and Michael addition reactions.  


In general, Lewis acid catalysts are metal-based compounds that owe their reactivity to a low-lying empty orbital. However, one potential Lewis acid that has received negligible attention as a catalyst is the carbocation. We have demonstrated the potential of the carbocation as a highly powerful Lewis acid catalyst for organic reactions. The stable and easily available triphenylmethyl (trityl) cation was found to be a highly efficient catalyst for the Diels-Alder reaction for a range of substrates. Catalyst loadings as low as 500?ppm, excellent yields, and good endo/exo selectivities were achieved. Furthermore, by changing the electronic properties of the substituents on the tritylium ion, the Lewis acidity of the catalyst could be tuned to control the outcome of the reaction. The ability of this carbocation as a Lewis acid catalyst was also further extended to the Michael reaction. PMID:24375806

Bah, Juho; Franzén, Johan



Proton conducting membrane using a solid acid  

NASA Technical Reports Server (NTRS)

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.

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



A New Instrument For Characterizing Solid Oxide Fuel Cell Catalysts  

E-print Network

temperature (typically 500°C - 800°C), it varies the gas environment in a controlled way, and it uses a precision robotic arm to touch the catalyst with a probe and take detailed measurements of the catalyst that can occur if multiple samples are used. This project fuses many disciplines: mechanical engineering


Superprotonic solid acids: Structure, properties, and applications  

NASA Astrophysics Data System (ADS)

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.

Boysen, Dane Andrew


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

NASA Technical Reports Server (NTRS)

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.

Mcalister, A. J.



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

NASA Technical Reports Server (NTRS)

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.

Mcalister, A. J.



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

NASA Technical Reports Server (NTRS)

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.

Mcalister, A. J.



Polyethylene as a nonvolatile solid cosolvent phase for catalyst separation and recovery.  


The studies described here show that a relatively low molecular weight, narrow polydispersity polyethylene (PE) wax (Polywax) can serve as a nontoxic and nonvolatile alternative to alkane solvents in monophasic catalytic organic reactions where catalysts and products are separated under biphasic conditions. In this application, a polymer that is a solid at room temperature substitutes for a conventional alkane solvent at ca. 80 °C. In addition to the advantages of being a nonvolatile, nontoxic, reusable solvent, this hydrocarbon polymer solvent, like heptane, can sequester nonpolar soluble polymer-bound catalysts after a reaction and separate them from products. The extent of this separation and its generality were studied using polyisobutylene (PIB)- and poly(4-dodecylstyrene)-bound dyes and PE-bound Pd allylic substitution catalysts, PIB-bound Pd cross-coupling catalysts, and PE- and PIB-bound metathesis catalysts. Catalytic reactions were effected using single-phase reaction mixtures containing Polywax with toluene, THF, or THF/DMF at ca. 80 °C. These solutions either separate into two liquid phases on addition of a perturbing agent or separate as a solid/liquid mixture on cooling. The hydrocarbon polymer-bound dyes or catalysts either separate into the hot liquid Polywax phase or coprecipitate with Polywax and are subsequently isolated as a nonvolatile Polywax solid phase that contains the dye or the recyclable catalyst. PMID:22924456

Yang, Yanfei; Priyadarshani, Nilusha; Khamatnurova, Tatyana; Suriboot, Jakkrit; Bergbreiter, David E



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


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

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



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...


Cathode catalysts for primary phosphoric acid fuel cells  

NASA Technical Reports Server (NTRS)

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.



Activity and structure of perovskites as diesel reforming catalysts for solid oxide fuel cells  

Microsoft Academic Search

Recent progress in developing perovskite materials as more cost-effective catalysts in autothermal reforming (ATR) of diesel fuel to hydrogen-rich reformate for solid oxide fuel cell (SOFC) application is reported. Perovskite-type metal oxides with B sites partially exchanged by ruthenium were prepared and evaluated under ATR reaction conditions. The hydrogen yield, reforming efficiency, and CO selectivity of these catalysts were investigated

Di-Jia Liu; Michael Krumpelt



Metal extraction from spent sulfuric acid catalyst through alkaline and acidic leaching  

Microsoft Academic Search

Spent catalyst from manufacture of sulfuric acid production (main elemental composition: 3.5% V, 0.63% Ni, 7.9% Fe and 9.64% Si) can be used as a secondary source of vanadium and nickel. Extraction of these metals was studied using two different leaching systems (alkaline and acidic). Statistical design of the experiments and ANOVA (analysis of variance) were performed in order to

A. Ognyanova; A. T. Ozturk; I. De Michelis; F. Ferella; G. Taglieri; A. Akcil; F. Vegliò



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

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

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



Acidity studies of fluid catalytic cracking catalysts by microcalorimetry and infrared spectroscopy  

Microsoft Academic Search

The acidic properties of a USY-based fluid catalytic cracking catalyst steamed at various severities and amorphous silica-alumina were investigated by microcalorimetry and infrared spectroscopy using pyridine adsorption at 473 K. Microcalorimetric measurements of the differential heat of pyridine adsorption versus adsorbate coverage revealed a heterogeneous acid site distribution for the catalysts. Besides showing the expected progressive decrease in the number

D. Chen; S. Sharma; J. A. Dumesic; N. Cardona Martinez; V. A. Bell; G. D. Hodge; R. J. Madon



Efficient hydrogen generation from sodium borohydride hydrolysis using silica sulfuric acid catalyst  

NASA Astrophysics Data System (ADS)

A heterogeneous acid catalyst, silica sulfuric acid, was prepared from silica gel (SiO2) and sulfuric acid (H2SO4). Addition of SO3H functional group to SiO2 has been confirmed through various characterization techniques. The effect of this heterogeneous acid catalyst on hydrogen generation from sodium borohydride hydrolysis reaction was studied for different ratios of catalyst to NaBH4 and at different temperatures. The catalyst exhibited high catalytic activity towards sodium borohydride hydrolysis reaction. The activation energy of the NaBH4 hydrolysis reaction in the presence of silica sulfuric acid was calculated to be the lowest (17 kJ mol-1) among reported heterogeneous catalysts till date.

Manna, Joydev; Roy, Binayak; Sharma, Pratibha



Degradation of perchlorate in water using aqueous multivalent titanium: effect of titanium type, ionic strength, and metal and solid catalysts.  


In this study, chemical degradation of perchlorate was investigated using partially oxidized titanium ions (Ti(II) and Ti(III)). Results of UV spectra showed that the patterns of absorbance at all ratios of F/Ti(0) were similar each other, except the lowest F/Ti(0) of 0.5 (25 mM F(-)) where mixture of Ti(II) and Ti(III) might be present, resulted in shift of the peak to wavelength of 480 nm. The rate of perchlorate degradation was fastest at lowest F/Ti(0) ratio. Among catalysts investigated, only rhenium enhanced the perchlorate degradation in the presence of Ti(II), but no effect of catalysts in Ti(III). In addition, high ionic strength did not enhance the perchlorate-Ti(III) reaction, but high acid concentration did. Addition of solid acid catalysts (SACs) to Ti(III) solution showed slower perchlorate degradation, probably due to decrease in Ti(III) concentration by adsorption onto SAC. Rate constants for perchlorate degradation in Ti(III) were twofold higher than in Ti(II) when 5 N HCl used. PMID:22633577

Park, Sung Hyuk; Batchelor, Bill; Lee, Chunwoo; Han, Dong Suk; Abdel-Wahab, Ahmed



Heterogeneous catalysis using a nanostructured solid acid resin based on lyotropic liquid crystals.  


The catalytic reactivity and selectivity of the first example of a nanostructured solid acid resin (1) are described. This new type of solid acid catalyst is formed by the self-assembly and copolymerization of two acidic lyotropic liquid crystals (LLCs), affording a columnar hexagonal polymer network with monodisperse nanochannels lined with sulfonic acid groups. The performance of this material as a heterogeneous catalyst was compared against that of two commercially available, amorphous sulfonic acid resins: Amberlyst-15 and Nafion NR50. Using the acid-catalyzed esterification of benzyl alcohol with 1-hexanoic acid in dry toluene as a test reaction, it was found that resin 1 displayed only slightly lower overall reactivity as compared to Amberlyst-15 and Nafion NR50 but more than an order of magnitude higher selectivity for the desired ester product over dibenzyl ether side-product. Control experiments revealed that the higher product selectivity is not due to differences in relative acidity between the nanostructured acid resin and the two amorphous resins. Instead, it appears that a large component of the enhanced selectivity is due to the regular nanostructure present in the LLC resin, which affords a much more uniform local acid microenvironment for reactions to occur. Resin 1 can also be recycled with almost complete recovery of catalytic activity and selectivity, and with essentially no leaching of reactive groups into the solution phase. PMID:14871076

Xu, Yanjie; Gu, Weiqiang; Gin, Douglas L




EPA Science Inventory

The reaction of neat 5- or 8-oxobenzopyran-2(1H)-ones with a variety of aromatic and heteroaromatic hydrazines are accelerated upon irradiation in a household microwave overn in the absence of any catalyst, solid support or solvent thus providing an environmentally friendly pathw...



EPA Science Inventory

The reaction of neat 5- or 8-oxobenzopyran-2(1H)-0nes with a variety of aromatic and heteroaromatic hydrazines are remarkably acceleterated upon irradiation in a household microwave oven in the absence of any catalyst, solid support or solvent. The approach provides an attractive...



EPA Science Inventory

The reaction of neat 5- or 8-oxobenzopyran-2(1H)-ones with a variety of aromatic and heteroaromatic hydrazines are remarkably accelerated upon irradiation in a household microwave oven in the absence of any catalyst, solid support or solvent. The approach provides an attractive a...


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


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

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



Method of performing sugar dehydration and catalyst treatment  


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.

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



Fe-pillared clay as a Fenton-type heterogeneous catalyst for cinnamic acid degradation.  


Fe-pillared montmorillonite has been used as a Fenton-type heterogeneous catalyst for the removal of cinnamic acid in water. The influences of the cinnamic acid, catalyst and H2O2 concentrations and pH on the removal rate of cinnamic acid have been studied. The results show that the efficiency of Fe-pillared montmorillonite is higher than that of the Fe ions in the homogeneous phase, and less sensitive to pH. PMID:16546315

Tabet, Djamel; Saidi, Mohamed; Houari, Mohamed; Pichat, Pierre; Khalaf, Hussein



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

NASA Astrophysics Data System (ADS)

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.

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



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

NASA Astrophysics Data System (ADS)

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.

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



Conversion of xylose into furfural using lignosulfonic acid as catalyst in ionic liquid.  


Preparation of biopolymer-based catalysts for the conversion of carbohydrate polymers to new energies and chemicals is a hot topic nowadays. With the aim to develop an ecological method to convert xylose into furfural without the use of inorganic acids, a biopolymer-derived catalyst (lignosulfonic acid) was successfully used to catalyze xylose into furfural in ionic acid ([BMIM]Cl). The characteristics of lignosulfonic acid (LS) and effects of solvents, temperature, reaction time, and catalyst loading on the conversion of xylose were investigated in detail, and the reusability of the catalytic system was also studied. Results showed that 21.0% conversion could be achieved at 100 °C for 1.5 h. The method not only avoids pollution from conventional mineral acid catalysts and organic liquids but also maked full use of a byproduct (lignin) from the pulp and paper industry, thus demonstrating an environmentally benign process for the conversion of carbohydrates into furfural. PMID:25007384

Wu, Changyan; Chen, Wei; Zhong, Linxin; Peng, Xinwen; Sun, Runcang; Fang, Junjie; Zheng, Shaobo




NSDL National Science Digital Library

There are two types of catalysis reactions: homogeneous and heterogeneous. In a homogeneous reaction, the catalyst is in the same phase as the reactants. In a heterogeneous reaction, the catalyst is in a different phase from the reactants. This activity addresses homogeneous catalysis.



Gallium(III) triflate: an efficient and a sustainable Lewis acid catalyst for organic synthetic transformations.  


Green chemical processes play a crucial role in sustainable development, and efficient recyclable catalysts that can be conveniently applied in various chemical reactions are the key elements for the development of sustainable synthetic processes. Many organic transformations rely on Lewis and Brønsted acid catalysts, and such molecules have been widely studied in organic synthesis. Over the years, researchers have looked for Lewis acid catalysts that provide high selectivity and high turnover frequency but are also stable in aqueous media and recoverable. Since the first preparation of trifluoromethanesulfonic acid by Hazeldine (triflic acid, HOTf), researchers have synthesized and used numerous metal triflates in a variety of organic reactions. Even though the rare earth metal triflates have played a major role in these studies, the majority of rare earth triflates lack one or more of the primary properties of sustainable catalysts: low cost and easy availability of the metals, easy preparation of triflates, aqueous/thermal stability, recyclability, and catalytic efficiency. In this Account, we describe the synthetic applications of Ga(OTf)(3) and its advantages over similar catalysts. Ga(OTf)(3) can be conveniently prepared from gallium metal or gallium chloride in excess of trifluoromethanesulfonic acid (triflic acid) under reflux. Among many Lewis acid catalysts recently studied, Ga(OTf)(3) is water tolerant and soluble and requires very low catalyst loading to drive various acid-catalyzed reactions including Friedel-Crafts alkylation, hydroxyalkylation, and acylation selectively and efficiently. In many reactions Ga(OTf)(3) demonstrated high chemo- and regioselectivity, high yields, excellent stability, and recyclability. We successfully synthesized many biologically active heterocycles and their fluoroanalogs under mild conditions. Many challenging reactions such as the ketonic Strecker reactions proceed efficiently via Ga(OTf)(3) catalysis. Because it is stable in water, this catalyst provides the opportunity to study substrates and develop new synthetic protocols in aqueous media, significantly reducing the production of hazardous waste from organic solvents and toxic catalyst systems. PMID:22148160

Prakash, G K Surya; Mathew, Thomas; Olah, George A



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


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

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



Heterogeneous catalysts for the transformation of fatty acid triglycerides and their derivatives to fuel hydrocarbons  

NASA Astrophysics Data System (ADS)

The results of studies devoted to the catalysts for transformation of fatty acid triglycerides and their derivatives to fuel hydrocarbons are presented and described systematically. Various approaches to the use of heterogeneous catalysts for the production of biofuel from these raw materials are considered. The bibliography includes 134 references.

Yakovlev, Vadim A.; Khromova, Sofia A.; Bukhtiyarov, Valerii I.



Glucose dehydration to 5-hydroxymethylfurfural in a biphasic system over solid acid foams.  


A solid acid foam-structured catalyst based on a binderless zirconium phosphate (ZrPO) coating on aluminum foam was prepared. The catalyst layer was obtained by performing a multiple washcoating procedure of ZrPO slurry on the anodized aluminum foam. The effect of the pretreatment of ZrPO, the concentration of the slurry, and the amount of coating on the properties of the foam was studied. The catalytic properties of the prepared foams have been evaluated in the dehydration of glucose to 5-hydroxymethylfurfural (HMF) in a biphasic reactor. The catalytic behavior of ZrPO foam-based catalysts was studied in a rotating foam reactor and compared with that of bulk ZrPO. The effect of a silylation procedure on the selectivity of the process was shown over bulk and foam catalysts. This treatment resulted in a higher selectivity due to the deactivation of unselective Lewis acid sites. Addition of methylisobutylketone leads to extraction of HMF from the aqueous phase and stabilization of the selectivity to HMF over bulk ZrPO. A more intensive contact of the foam with the aqueous and organic phases leads to an increase in the selectivity and resistance to deactivation of the foam in comparison with a bulk catalyst. PMID:23616489

Ordomsky, Vitaly V; van der Schaaf, John; Schouten, Jaap C; Nijhuis, T Alexander



Removal of Cl adsorbed on Mn-Ce-La solid solution catalysts during CVOC combustion.  


Mn-Ce-La oxide-mixed catalysts prepared by the method of complexation followed by calcination at 750°C were tested in the catalytic combustion of chlorobenzene (CB) taken as a model of chlorinated aromatics. XRD analyses show that Mn and La enter CeO2 matrix with a fluorite-like structure to form solid solution. The catalysts with high ratio of Mn/Mn+Ce+La exhibit high activity for CB combustion, due to high oxygen mobility. For all Mn-Ce-La catalysts, deactivation due to Cl adsorption is observed at different temperatures, depending on composition. At 330°C or higher temperature, the removal of Cl species from the surface in the forms of Cl2 (produced through Deacon reaction) and HCl (produced through hydrolysis of Cl) occurs and the activity of catalysts for CB combustion becomes thus stable. Either the addition of water or the increase in gaseous oxygen concentration can promote the removal of Cl species, and thus to increase the activity for CB combustion. High stable activity of Mn-Ce-La catalysts can be related to the combination of good oxidation and Deacon reaction performances. PMID:24863800

Wang, Xingyi; Ran, Le; Dai, Yu; Lu, Yuanjiao; Dai, Qiguang



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


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

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



Molybdenum phosphosulfide: an active, Acid-stable, Earth-abundant catalyst for the hydrogen evolution reaction.  


Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non-noble-metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed-metal alloy catalysts are well-known, MoP|S represents a more uncommon mixed-anion catalyst where synergistic effects between sulfur and phosphorus produce a high-surface-area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water-splitting cells. PMID:25359678

Kibsgaard, Jakob; Jaramillo, Thomas F



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

NASA Astrophysics Data System (ADS)

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.

Buelte, Steve


Bifunctional organic polymeric catalysts with a tunable acid-base distance and framework flexibility.  


Acid-base bifunctional organic polymeric catalysts were synthesized with tunable structures. we demonstrated two synthesis approaches for structural fine-tune. In the first case, the framework flexibility was tuned by changing the ratio of rigid blocks to flexible blocks within the polymer framework. In the second case, we precisely adjusted the acid-base distance by distributing basic monomers to be adjacent to acidic monomers, and by changing the chain length of acidic monomers. In a standard test reaction for the aldol condensation of 4-nitrobenzaldehyde with acetone, the catalysts showed good reusability upon recycling and maintained relatively high conversion percentage. PMID:25267260

Chen, Huanhui; Wang, Yanan; Wang, Qunlong; Li, Junhui; Yang, Shiqi; Zhu, Zhirong



Bifunctional Organic Polymeric Catalysts with a Tunable Acid-Base Distance and Framework Flexibility  

NASA Astrophysics Data System (ADS)

Acid-base bifunctional organic polymeric catalysts were synthesized with tunable structures. we demonstrated two synthesis approaches for structural fine-tune. In the first case, the framework flexibility was tuned by changing the ratio of rigid blocks to flexible blocks within the polymer framework. In the second case, we precisely adjusted the acid-base distance by distributing basic monomers to be adjacent to acidic monomers, and by changing the chain length of acidic monomers. In a standard test reaction for the aldol condensation of 4-nitrobenzaldehyde with acetone, the catalysts showed good reusability upon recycling and maintained relatively high conversion percentage.

Chen, Huanhui; Wang, Yanan; Wang, Qunlong; Li, Junhui; Yang, Shiqi; Zhu, Zhirong



Solid-state actinide acid phosphites from phosphorous acid melts  

NASA Astrophysics Data System (ADS)

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.

Oh, George N.; Burns, Peter C.



Chance and necessity in the selection of nucleic acid catalysts  

NASA Technical Reports Server (NTRS)

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.

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



Synthesis of chiral ?- substituted ?-hydroxy acid derivatives on solid support  

Microsoft Academic Search

Enantioselective aldol condensation using solid supported chiral auxiliary was used for the synthesis of ?-substituted-?-hydroxy acid and ester. The solid phase synthesis proceeded with high degree of enatioselectivity, as is observed in solution chemistry.

Ashok V Purandare; Sesha Natarajan



Structural analysis of nickel doped cerium oxide catalysts for fuel reforming in solid oxide fuel cells  

NASA Astrophysics Data System (ADS)

As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO 2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.

Cavendish, Rio


Cyclobutane amino acids and peptidomimetics, parallel catalyst screening for aziridination  

E-print Network

; and, the octapeptide synthesized in this study adapts an P-hairpin secondary structure, as evidenced by CD and 2D NMR. The second project is parallel catalyst screening for aziridination of olefins. Since aziridines are versatile intermediates...

Li, Shih-ming



Toluene and chlorobenzene dinitration over solid H3PO4/MoO3/SiO2 catalyst.  


A new catalyst, H(3)PO(4)/MoO(3)/SiO(2), was prepared by modification of MoO(3)/SiO(2) using phosphoric acid. The characterization of the catalyst was performed using Infrared and Raman Spectroscopy, potentiometric titration and nitrogen adsorption-desorption methods. Molybdenum oxides were identified along with phosphomolybdic acid and polymolybdates on the modified surface. The suitability of the catalysts for toluene and chlorobenzene nitration in continuous process was examined. Toluene is effectively nitrated to dinitrotoluene (DNT) in one-stage process (96 wt.% of DNT in the product) and in mild conditions i.e. at room temperature and only with ten-fold excess of nitric acid. In chlorobenzene nitration only twelve-fold excess of nitric acid is needed to obtain as high yield as 95 wt.%. Most importantly, the novel catalysts we have developed, provide the opportunity for sulfuric acid- free nitration of aromatic compounds. PMID:21885194

Adamiak, Joanna; Kalinowska-Alichnewicz, Dorota; Szadkowski, Micha?; Skupi?ski, Wincenty



Improved anode catalysts for coal gas-fueled phosphoric acid fuel cells  

NASA Astrophysics Data System (ADS)

The development, optimization and demonstration of contaminant-tolerant anode catalyst formulations for phosphoric acid fuel cells is the overall objective of this project. The goal is to develop supported catalyst systems that will not only be able to operate on feed gases containing high levels of CO, H2S, and COS, but will, in fact, encourage the shift reaction to convert the CO to additional H2 or anodically convert CO to CO2, boosting the power content of the fuel gas. Of CO conversion is not feasible, a secondary goal is to demonstrate CO- and H2S-tolerant catalysts so that gas cleanup requirements can be minimized. Upper limits for individual contaminant concentrations and mixtures of contaminant gases that can be tolerated by the advanced anode catalysts will be determined. This quarter, the two catalysts selected for testing were Pt-Ti-Ru and Pt-Ti-ZA, hydrogen/hydrogen cell testing continued.

Kackley, Nancy; Kosek, John A.



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

SciTech Connect

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.

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




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...


Effect of calcination temperature on the activity of solid Ca/Al composite oxide-based alkaline catalyst for biodiesel production.  


A solid Ca/Al composite oxide-based alkaline catalyst containing Ca(12)Al(14)O(33) and CaO was prepared by chemical synthesis and thermal activation from sodium aluminate solution and calcium hydroxide emulsion. The effect of calcination temperatures ranging from 120 °C to 1000 °C on activity of the catalyst was investigated. The catalyst calcined at 600 °C showed the highest activity with >94% yield of fatty acid methyl esters (i.e. biodiesel) when applied to the transesterification of rapeseed oil at a methanol:oil molar ratio of 15:1 at 65 °C for 3h. Structure and properties of the catalyst were studied and the characterizations with XRD, TGA, FTIR, BET, and SEM demonstrated that the performance of the catalyst was closely related to its specific surface area and crystalline structure. In particular, the generation of crystalline Ca(12)Al(14)O(33) improved the catalytic activity due its synergistic effect with CaO. PMID:23196252

Meng, Yong-Lu; Wang, Bo-Yang; Li, Shu-Fen; Tian, Song-Jiang; Zhang, Min-Hua



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


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

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



Highly efficient tetradentate ruthenium catalyst for ester reduction: especially for hydrogenation of Fatty Acid esters.  


A new tetradentate ruthenium complex has been developed for hydrogenation of esters. The catalyst's structure features a pyridinemethanamino group and three tight chelating five-membered rings. The structure character is believed to be responsible for its high stability and high carbonylation-resistant properties. Thus, this catalyst shows outstanding performance in the catalytic hydrogenation of a variety of esters, especially for fatty acid esters, which may be used in practical applications. New insight on designing hydrogenation catalyst for reducing esters to alcohols has been provided through theoretical calculations. PMID:25582610

Tan, Xuefeng; Wang, Yan; Liu, Yuanhua; Wang, Fangyuan; Shi, Liyang; Lee, Ka-Ho; Lin, Zhenyang; Lv, Hui; Zhang, Xumu



Evaluating acid and base catalysts in the methylation of milk and rumen fatty acids with special emphasis on conjugated dienes and total trans fatty acids  

Microsoft Academic Search

Milk analysis is receiving increased attention. Milk contains conjugated octadecadienoic acids (18?2) purported to be anticarcinogenic,\\u000a low levels of essential fatty acids, and trans fatty acids that increase when essential fatty acids are increased in dairy rations. Milk and rumen fatty acid methyl esters\\u000a (FAME) were prepared using several acid-(HCl, BF3, acetyl chloride, H2SO4) or base-catalysts (NaOCH3, tetramethylguanidine, diazomethane), or

John K. G. Kramer; Vivek Fellner; Michael E. R. Dugan; Frank D. Sauer; Magdi M. Mossoba; Martin P. Yurawecz



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


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 C. and preferably from 250 to 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.

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



Oligomerization of 2-methylpropene and transformation of 2,4,4-trimethyl-2-pentene over supported and unsupported perfluorinated resinsulfonic acid catalysts  

SciTech Connect

Oligomerization of 2-methylpropene was studied with two types of supported (on alumina and on silicon carbide) as well neat perfluorinated resinsulfonic acid catalysts. The heterogeneous reactions were carried out over the solid acid catalysts in a continuous flow reactor at temperatures between 85 and 170 C under atmospheric pressure. Under the studied conditions (85 to 105 C, 1 atm pressure, WHSV:1-3 g/g {center dot} h) all catalysts studied are suitable for oligomerization of 2-methyl-propene. Product distributions show regular temperature dependence: upon increasing temperature the molecular weight of oligomers decreases, with no difference in the selectivity of the catalysts. Transformation of 2,4,4-trimethyl-2-pentene in the liquid phase at room temperature shows surprising selectivity using either the hydrated or dehydrated forms of the resinsulfonic acids. In the case of the hydrated forms of the acids, only double bond isomerization takes place. With dehydrated acids oligomerization as well as isomerization occurs. Above 50 C the selectivity is lost.

Bucsi, I.; Olah, G.A. (Univ. of Southern California, University Park, Los Angeles (United States))



Phosphotungstic acid supported on magnetic nanoparticles as an efficient reusable catalyst for epoxidation of alkenes  

SciTech Connect

Highlights: ? Phosphotungstic acid supported on functionalized cobalt ferrite was prepared. ? Silica coated cobalt ferrite nanoparticles were used as support. ? This composite was successfully used as catalyst for epoxidation of alkenes. ? Oxidation reactions were carried out in the presence of t-BuOOH as oxidant. ? The catalyst can be readily separated from solution by magnetic field. -- Abstract: A new magnetically separable catalyst consisting of phosphotungstic acid supported on imidazole functionalized silica coated cobalt ferrite nanoparticles was prepared. The synthesized catalyst was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). This immobilized phosphotungstic acid was shown to be an efficient heterogeneous catalyst for the epoxidation of various alkenes using tert-butylhydroperoxide (t-BuOOH) as oxidant. The catalyst is readily recovered by simple magnetic decantation and can be recycled several times with no significant loss of catalytic activity.

Kooti, M., E-mail: [Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz 61357- 43169 (Iran, Islamic Republic of); Afshari, M. [Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz 61357- 43169 (Iran, Islamic Republic of)] [Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz 61357- 43169 (Iran, Islamic Republic of)



Characterisation of coke from FCC catalysts by solid state {sup 13}C NMR and mass spectrometry  

SciTech Connect

Coke has been concentrated by demineralisation from deactivated FCC catalysts from both refinery operations with actual feeds and MAT tests using n-hexadecane to facilitate detailed characterisation by solid state {sup 13}C NMR and mass spectrometry. All the catalysts investigated contained about 1% w/w carbon. As for solid fuels, the use of a low-field spectrometer for solid state {sup 13}C NMR in conjunction with the single pulse excitation (SPE or Bloch decay) technique has enabled quantitative carbon skeletal parameters to be obtained for the cokes. Internal standard measurements demonstrated that most of the carbon was observed by SPE and, therefore, NMR-invisible graphitic layers are not thought to be major structural features of the cokes. Differences in feedstock composition were reflected in the structure of the refinery cokes with the aromatic nuclei from a residue feed (5% Conradson carbon) corresponding to 15-20 peri-condensed aromatic rings and being more highly condensed than those from a hydrotreated vacuum gas oil. Mass spectrometry (EI, CI and FIMS) has confirmed that the refinery cokes are highly condensed, but those obtained from n-hexadecane in the MAT tests displayed significant aliphatic character.

Andresen, J.M.; McGhee, B.; Snape, C.E. [Univ. of Strathclyde, Glasgow (United Kingdom)] [and others



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


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.

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



Comparison of different Lewis acid supported on hydroxyapatite as new catalysts of Friedel–Crafts alkylation  

Microsoft Academic Search

ZnCl2, NiCl2 and CuCl2 supported on hydroxyapatite (HAP), as a new solid support, catalyse the Friedel–Crafts alkylation of benzene, toluene and p-xylene by benzyl chloride. The reaction proceeds selectively to monoalkyl-compounds and in a short reaction time. The best catalytic activities were observed with the zinc catalysts.

Rachid Tahir; Rachid Nazih



Reductive desorption of sulfuric acid formed on the carbon catalyst in flue gas desulfurization (FGD)  

Microsoft Academic Search

Reductive desorption of sulfuric acid formed on the carbon catalyst in flue gas desulfurization (FGD) by heating with hydrogen at 3: 200°C converted the acid to gas-phase sulfur dioxide with a significant loss of the acid to hydrogen sulfide and elemental sulfur. These side reactions were suppressed and the temperature required for SOâ recovery was reduced by impregnating the charcoal

S. Yoshizawa; A. Karagiri; K. Watanabe



Organo-niobate Ionic Liquids: Synthesis, Characterization and Application as Acid Catalyst in Pechmann Reactions  

PubMed Central

The combinations of 1-butyl-3-methylimidazolium chloride with NbCl5 yielded ionic mixtures with different melting point temperatures and acidity depending on the niobium molar fraction. The mixtures were characterized by thermal (DSC) and spectroscopic (FT-IR and 1H NMR) analysis. The Pechmann reactions of different phenols with ethylacetoacetate, producing coumarins, was used as model to evaluate the catalytic behavior of these mixtures as acid Lewis catalyst. These reactions were carried out using acidic mixtures of 60 mol%.

Soares, Valerio C. D.; Alves, Melquizedeque B.; Souza, Ernesto R.; Pinto, Ivana O.; Rubim, Joel C.; Andrade, Carlos Kleber Z.; Suarez, Paulo A. Z.



Effect of nickel on the acidity and hydrodesulfurization (HDS) activity of supported molybdate catalysts  

SciTech Connect

The effect of nickel on the acidity and hydrodesulfurization (HDS) activity of supported molybdate catalysts, i.e., 12% MoO/sub 3//Al/sub 2/O/sub 3/ and 3% NiO/13% MoO/sub 3//Al/sub 2/O/sub 3/ prepared by impregnating ..gamma..-Al/sub 2/O/sub 3/ with aqueous ammonium molybdate and nickel nitrate and calcining the samples at 500/sup 0/C, was studied by comparing total and irreversible ammonia adsorption on pure support and nickel-promoted and unpromoted MoO/sub 3/ catalysts at 50/sup 0/-300/sup 0/C and 50-630 mm Hg NH/sub 3/, determining strength distribution of acid sites on the catalyst surface by titration of color indicators with n-butylamine and measuring the catalyst activity in thiophene HDS in a continuous flow reactor at 400/sup 0/C, 1 atm, and 45:1 hydrogen/thiophene molar ratio. Incorporation of MoO/sub 3/ increased both the over-all and the strong acidity of alumina. Promotion of MoO/sub 3//Al/sub 2/O/sub 3/ with NiO further increased the over-all acidity but reduced the concentration of strong acidic sites (pKa less than or equal to -2.4) in favor of intermediate-strength (pKa +2 to +5) sites. The Ni-promoted catalyst had a lower initial HDS activity but a considerably higher steady-state activity than MoO/sub 3//Al/sub 2/O/sub 3/. Apparently thiophene HDS occurs both on strong Broensted (MoO/sub 3/) and Lewis (MoS/sub 2/) acid sites typical of fresh, unpromoted and aged, promoted catalysts, respectively.

Laine, J.; Brito, J.; Yunes, S.



Supported organoiridium catalysts for alkane dehydrogenation  


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.

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



Liquid phase nitration of benzene over supported ammonium salt of 12-molybdophosphoric acid catalysts prepared by sol-gel method.  


A mild and clean liquid nitration of benzene with 65% nitric acid as nitrating agent over silica supported ammonium salt of 12-molybdophosphoric acid catalysts has been investigated. These catalysts with different loadings were prepared by sol-gel method and characterized by X-ray diffraction (XRD) and FTIR spectra. The acidity of these catalysts was measured by the potentiometric titration method. The XRD and IR analysis revealed that supported catalysts possess the Keggin structure which is similar to 12-molybdophosphoric acid. And it can be found that the supported catalysts had high nitration reaction catalytic activity and selectivity over nitrobenzene. The effects of various parameters such as nitric acid/benzene volume ratio, temperature and time of reaction have also been systematically studied. PMID:20185228

Gong, Shuwen; Liu, Lijun; Cui, Qingxin; Ding, Junhong



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

NASA Astrophysics Data System (ADS)

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.

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



Oxidizing of ferulic acid with the use of polyoxometalates as catalysts  

NASA Astrophysics Data System (ADS)

The kinetics of catalytic oxidation for ferulic acid with polyoxometalates used as catalysts was studied. The effect of pH and concentrations of the principal reacting components on the process kinetics was studied. A kinetic scheme of oxidation is proposed, and the values of a number of kinetic parameters of the process are determined.

Povarnitsyna, T. V.; Popova, N. R.; Bogolitsyn, K. G.; Beloglazova, A. L.; Pryakhin, A. N.; Lunin, V. V.



Homogeneous and Supported Niobium Catalysts as Lewis Acid and Radical Catalysts  

SciTech Connect

The synthesis of tetrachlorotetraphenylcyclopentadienyl group 5 metal complexes has been accomplished through two routes, one a salt metathesis with lithiumtetraphenylcyclopentadiende and the other, reaction with trimethyltintetraphenylcyclopentadiene. The reactants and products have been characterized by {sup 1}H and {sup 13}C({sup 1}H) NMR spectroscopy. The niobium complex promotes the silylcyanation of butyraldehyde. The grafting of metal complexes to silica gel surfaces has been accomplished using tetrakisdimethylamidozirconium as the metal precursor. The most homogeneous binding as determined by CP-MAS {sup 13}C NMR and infrared spectroscopy was obtained with drying at 500 C at 3 mtorr vacuum. The remaining amido groups can be replaced by reaction with alcohols to generate surface bound metal alkoxides. These bound catalysts promote silylcyanation of aryl aldehydes and can be reused three times with no loss of activity.

Wayne Tikkanen



Hydrometallurgical route to recover molybdenum, nickel, cobalt and aluminum from spent hydrotreating catalysts in sulphuric acid medium.  


This work describes a hydrometallurgical route for processing spent commercial catalysts (CoMo and NiMo/Al2O3), for recovering the active phase and support components. They were initially pre-oxidized (500 degrees C, 5h) in order to eliminate coke and other volatile species present. Pre-oxidized catalysts were dissolved in H2SO4 (9molL-1) at approximately 90 degrees C, and the remaining residues separated from the solution. Molybdenum was recovered by solvent extraction using tertiary amines. Alamine 304 presented the best performance at pH around 1.8. After this step, cobalt (or nickel) was separated by adding aqueous ammonium oxalate in the above pH. Before aluminum recovery, by adding NaOH to the acid solution, phosphorus (H2PO4-) was removed by passing the liquid through a strong anion exchange column. Final wastes occur as neutral and colorless sodium sulphate solutions and the insoluble solid in the acid leachant. The hydrometallurgical route presented in this work generates less final aqueous wastes, as it is not necessary to use alkaline medium during the metal recovery steps. The metals were isolated in very high yields (>98wt.%). PMID:18400377

Valverde, Ivam Macedo; Paulino, Jéssica Frontino; Afonso, Julio Carlos



When gold meets chiral Brønsted acid catalysts: extending the boundaries of enantioselective gold catalysis.  


This review describes the development in the use of Au(I)/Brønsted acid binary catalytic systems to enable an enantioselective transformation in one-pot that cannot be achieved by gold catalysts alone. The examples discussed herein are promising since apart from using chiral ligands there exists a possibility of using chiral Brønsted acids. Clearly, the horizon for enantioselective gold catalysis has been expanded as more options to make the gold-catalyzed reactions enantioselective have become available. PMID:25177929

Inamdar, Suleman M; Konala, Ashok; Patil, Nitin T



The behavior of palladium catalysts in direct formic acid fuel cells  

NASA Astrophysics Data System (ADS)

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.

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


Biodiesel production from waste cooking oil using a heterogeneous catalyst from pyrolyzed rice husk.  


A solid acid catalyst was prepared by sulfonating pyrolyzed rice husk with concentrated sulfuric acid, and the physical and chemical properties of the catalyst were characterized in detail. The catalyst was then used to simultaneously catalyze esterification and transesterification to produce biodiesel from waste cooking oil (WCO). In the presence of the as-prepared catalyst, the free fatty acid (FFA) conversion reached 98.17% after 3h, and the fatty acid methyl ester (FAME) yield reached 87.57% after 15 h. By contrast, the typical solid acid catalyst Amberlyst-15 obtained only 95.25% and 45.17% FFA conversion and FAME yield, respectively. Thus, the prepared catalyst had a high catalytic activity for simultaneous esterification and transesterification. In addition, the catalyst had excellent stability, thereby having potential use as a heterogeneous catalyst for biodiesel production from WCO with a high FFA content. PMID:24405650

Li, Ming; Zheng, Yan; Chen, Yixin; Zhu, Xifeng



Hydrothermal conversion of cellulose into lactic acid with nickel catalyst  

Microsoft Academic Search

Utilization of biomass has become a major topic of research around the world. One promising aspect of utilization is production\\u000a of lactic acid from carbohydrate biomass. Our previous study showed that lactic acid can be formed from glucose and cellulose\\u000a by alkaline hydrothermal reactions, but the yield of lactic acid was low, particular for cellulose. In this study, an efficient

Feng-Wen Wang; Zhi-Bao Huo; Yuan-Qing Wang; Fang-Ming Jin



Hydrogenation of biofuels with formic acid over a palladium-based ternary catalyst with two types of active sites.  


A composite catalyst including palladium nanoparticles on titania (TiO2) and on nitrogen-modified porous carbon (Pd/TiO2@N-C) is synthesized from palladium salts, tetrabutyl titanate, and chitosan. N2 sorption isotherms show that the catalyst has a high BET surface area (229?m(2) ?g(-1)) and large porosity. XPS and TEM characterization of the catalyst shows that palladium species with different chemical states are well dispersed across the TiO2 and nitrogen-modified porous carbon, respectively. The Pd/TiO2@N-C catalyst is very active and shows excellent stability towards hydrogenation of vanillin to 2-methoxy-4-methylphenol using formic acid as hydrogen source. This activity can be attributed to a synergistic effect between the Pd/TiO2 (a catalyst for dehydrogenation of formic acid) and Pd/N-C (a catalyst for hydrogenation of vanillin) sites. PMID:24861954

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



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

E-print Network

. If this correction is not precise, the glue line will be uncured or overcured, and this will result in poor bond­1569, 2007 Key words: adhesives; catalysts; gelation; resins; thermo- sets INTRODUCTION The pH value, solid bond strength, the press time and temperature must be adjusted for the pH envi- ronment

Wang, Siqun


Study of the parameters controlling the enantio-differentiating ability of asymmetrically modified solid catalysts for the hydrogenation of ?-ketoesters  

Microsoft Academic Search

The enantio-differentiating hydrogenation of ?-ketoesters was carried out over asymmetrically modified solid catalysts. The parameters affecting the enantiomer excess (ee) were investigated and the results were compared with those of the hydrogenation of methyl acetoacetate and 2-octanone reported in the literature. The highest value of enantiomer excess of 51% was attained for the hydrogenation of methyl 4-oxopentanoate over a tartaric

Tsutomu Osawa; Eri Mieno; Tadao Harada; Osamu Takayasu



Tetraphosphine Linker Scaffolds with a Tetraphenyltin Core for Superior Immobilized Catalysts: A Solid-State NMR Study  

E-print Network

the mechanism of the phosphonium formation in more detail by utilizing solid-state NMR spectroscopy. It has also been a point of interest to study the linkers and catalysts under realistic conditions, in the presence of solvents. Therefore, HRMAS (high...

Perera, Melanie Ingrid




EPA Science Inventory

NRMRL-CIN-1437A Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. "Solid-State Synthesis of Heterocyclic Hydrazones using Microwaves under Catalyst-free Conditions http:///" Fifth International Electronic Conference on Synthetic Organic Chemistry, h...



EPA Science Inventory

NRMRL-CIN-1605 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Solid-State Synthesis of Heterocyclic Hydrazones using Microwaves under Catalyst-free Conditions. Green Chemistry (White, J.D. (Ed.), Cambridge, United Kingdom: Royal Society of Chemistry) (4):35-38 (2002). ...


Efficient hydrolysis of cellulose over a novel sucralose-derived solid acid with cellulose-binding and catalytic sites.  


A new sucralose-derived solid acid catalyst (SUCRA-SO3H), containing -Cl and -SO3H functional groups, has been shown to be highly effective for hydrolyzing ?-1,4-glucans, completely hydrolyzing cellobiose (1) into glucose (2) in 3 h and converting the microcrystalline cellulose pretreated by the ionic liquid into glucose (2) with a yield of around 55% and a selectivity of 98% within 24 h at a relatively moderate temperature (393K). The enhanced adsorption capacity that the catalyst has for glucan by virtue of the presence of chloride groups that act as cellulose-binding sites offers the possibility of resolving the existing bottleneck in heterogeneous catalysis to hydrolyze cellulose, namely, the low accessibility of cellulose to the reaction position in typical solid catalysts. The apparent activation energy for hydrolysis of cellobiose (1) with SUCRA-SO3H was 94 kJ/mol, which was much lower than that with sulfuric acid (133 kJ/mol) and the corresponding sucrose-derived catalyst (SUCRO-SO3H) without chlorine groups (114 kJ/mol). PMID:24512554

Hu, Shuanglan; Smith, Thomas John; Lou, Wenyong; Zong, Minhua



Tritium labeling of amino acids and peptides with liquid and solid tritium  

SciTech Connect

Amino acids and peptides were labeled with liquid and solid tritium at 21/degree/K and 9/degree/K. At these low temperatures radiation degradation is minimal, and tritium incorporation increases with tritium concentration and exposure time. Ring saturation in L-phenylalanine does not occur. Peptide linkage in oligopeptides is stable toward tritium. Deiodination in 3-iodotyrosine and 3,5-diiodotyrosine occurs readily and proceeds in steps by losing one iodine atom at a time. Nickel and noble metal supported catalysts when used as supports for dispersion of the substrate promote tritium labeling at 21 K. Our study shows that both liquid and solid tritiums are potentially useful agents for labeling peptides and proteins.

Souers, P.C.; Coronado, P.R.; Peng, C.T.; Hua, R.L.



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

NASA Astrophysics Data System (ADS)

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.

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



Improved anode catalysts for coal gas-fueled phosphoric acid fuel cells  

NASA Astrophysics Data System (ADS)

The feasibility of adapting phosphoric acid fuel cells to operate on coal gas fuels containing significant levels of contaminants such as CO, H2S and COS was investigated. The overall goal was the development of low-cost, carbon-supported anode fuel cell catalysts that can efficiently operate with a fossil fuel-derived hydrogen gas feed contaminated with carbon monoxide and other impurities. This development would reduce the cost of gas cleanup necessary in a coal gas-fueled PAFC power plant, thereby reducing the final power cost of the electricity produced. The problem to date was that the contaminant gases typically adsorb on catalytic sites and reduce the activity for hydrogen oxidation. An advanced approach investigated was to modify these alloy catalyst systems to operate efficiently on coal gas containing higher levels of contaminants by increasing the alloy catalyst impurity tolerance and ability to extract energy from the CO present through (1) generation of additional hydrogen by promoting the CO/H2 water shift reaction or (2) direct oxidation of CO to CO2 with the same result. For operation on anode gases containing high levels of CO, a Pt-Ti-Zn and Pt-Ti-Ni anode catalyst showed better performance over a Pt baseline or G87A-17-2 catalyst. The ultimate aim was to allow PAFC-based power plants to operate on coal gas fuels containing increased contaminant concentrations, thereby decreasing the need for and cost of rigorous coal gas cleanup procedures.

Kackley, N. D.; McCatty, S. A.; Kosek, J. A.



Poly-benzylic ammonium chloride resins as solid catalysts for fructose dehydration.  


5-hydroxymethylfurfural (HMF) is one of the most promising platform molecules, and can be converted into a variety of interesting chemicals. The production of HMF is essentially targeted at bulk chemicals downstream, such as chemicals for the fuels and plastics industries. One critical challenge in HMF production processes is the link to further value-adding reactions in a simple and efficient way (e.g., fewer isolation and purification steps). Herein, a novel poly-benzyl ammonium chloride (PBnNH3 Cl) resin is developed as a highly efficient and stable catalyst for dehydration of carbohydrates into HMF. In the isopropanol system, PBnNH3 Cl produces high purity HMF that is suitable as feedstock for oxidation to 2,5-furandicarboxylic acid (FDCA). The excellent catalytic properties together with its easy synthesis, low cost, and nontoxic nature make this poly-ammonium resin a promising catalyst for the development of new and efficient processes for biomass-based chemicals. PMID:24903397

Teong, Siew Ping; Yi, Guangshun; Cao, Xueqin; Zhang, Yugen



Effect of deactivation and reactivation of palladium anode catalyst on performance of direct formic acid fuel cell (DFAFC)  

Microsoft Academic Search

In the present study, degradation and recovery in cell performance of direct formic acid fuel cells (DFAFCs) are investigated. For DFAFC tests, palladium (Pd) and platinum (Pt) are used as anode and cathode catalysts, respectively, and are applied to a Nafion membrane by catalyst-coated membrane (CCM) spraying. As multiple repeated DFAFC operations are performed, the cell performance of DFAFC is

S. M. Baik; Jonghee Han; Jinsoo Kim; Yongchai Kwon



Characterization of acidic properties of microporous and mesoporous zeolite catalysts using TGA and DSC  

SciTech Connect

Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied for characterizing the acidic properties of microporous and mesoporous zeolite catalysts through temperature-programmed desorption (TPD) of n-butylamine (n-BA) as a base probe molecule. A flow system was designed with heating and evacuation capability for preparing the n-BA adsorbed sample. In the TGA, n-BA desorption at different temperatures represents the interaction with surface acidic sites of different strength. The acid sites corresponding to base desorption at 100-240{degrees}C, 240-340{degrees}C, and 340-500{degrees}C, were classified as weak, intermediate, and strong acid sites, respectively. DSC indicates the endothermic nature of the differential thermogravimetric peaks (observed from TGA) in the above temperature regimes, consuming the TPD data. The microporous zeolites examined include three proton-form mordenites, three proton-form and metal-ion exchanged Y-zeolites, and four noble metal catalysts supported on mordenite and Y-zeolite. Four mesoporous zeolites were synthesized and examined by the same TPD method. Both the total acidity (mmol/g) and acid strength distribution depend on the zeolite VAX, Si/Al ratio, and metal loading. Ni and La ion-exchange decreased the strong acid sites. Pt and Pd loading on an HY decreased the strong acid sites but their loading on an H-mordenite had little effect on its strong acid sites. Mesoporous zeolites showed lower acidity and lower fraction of strong acid sites compared to HY and H-mordenites. However, the acidity of mesoporous zeolites strongly depends on the aluminum source compounds used in the hydrothermal synthesis of the zeolites.

Song, Chunshan; Lai, Wei-Chuan; Schmitz, A.D. [Pennsylvania State Univ., University Park, PA (United States)] [and others



Catalyst-assisted solution-liquid-solid synthesis of CdS/CdSe nanorod heterostructures.  


We report the synthesis and characterization of axial nanorod heterostructures composed of cadmium selenide (CdSe) and cadmium sulfide (CdS). The synthesis employs a solution-liquid-solid (SLS) mechanism with the assistance of bismuth nanocrystals adhered to a substrate (silicon or a III-V semiconductor). Transmission electron microscopy (TEM) and diffraction studies show that CdSe and CdS segments exhibit the wurtzite (hexagonal) crystal structure with <5% stacking faults. Both of these segments grow along the [002] direction with an epitaxial interface between them. Energy-dispersive X-ray (EDX) spectrometry using a high-resolution TEM operating in scanning mode confirms the alloy-free composition modulation in the nanorod heterostructures, showing that Se and S are localized in the CdSe and CdS portions of the nanorod heterostructures, respectively. This study demonstrates that SLS synthesis provides an alternate route to prepare axial nanorod heterostructures that have been difficult to generate using either vapor-liquid-solid growth or catalyst-free solution-phase synthesis. PMID:17199292

Ouyang, Lian; Maher, Kristin N; Yu, Chun Liang; McCarty, Justin; Park, Hongkun



Airborne concentrations of metals and total dust during solid catalyst loading and unloading operations at a petroleum refinery.  


Workers handle catalysts extensively at petroleum refineries throughout the world each year; however, little information is available regarding the airborne concentrations and plausible exposures during this type of work. In this paper, we evaluated the airborne concentrations of 15 metals and total dust generated during solid catalyst loading and unloading operations at one of the largest petroleum refineries in the world using historical industrial hygiene samples collected between 1989 and 2006. The total dust and metals, which included aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, platinum, silicon, silver, vanadium, and zinc, were evaluated in relation to the handling of four different types of solid catalysts associated with three major types of catalytic processes. Consideration was given to the known components of the solid catalysts and any metals that were likely deposited onto them during use. A total of 180 analytical results were included in this analysis, representing 13 personal and 54 area samples. Of the long-term personal samples, airborne concentrations of metals ranged from <0.001 to 2.9mg/m(3), and, in all but one case, resulted in concentrations below the current U.S. Occupational Safety and Health Administration's Permissible Exposure Limits and the American Conference of Governmental Industrial Hygienists' Threshold Limit Values. The arithmetic mean total dust concentration resulting from long-term personal samples was 0.31mg/m(3). The data presented here are the most complete set of its kind in the open literature, and are useful for understanding the potential exposures during solid catalyst handling activities at this petroleum refinery and perhaps other modern refineries during the timeframe examined. PMID:22177528

Lewis, Ryan C; Gaffney, Shannon H; Le, Matthew H; Unice, Ken M; Paustenbach, Dennis J



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

PubMed Central

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

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



Geminal Brønsted Acid Ionic Liquids as Catalysts for the Mannich Reaction in Water  

PubMed Central

Quaternary ammonium geminal Brønsted acid ionic liquids (GBAILs) based on zwitterionic 1,2-bis[N-methyl-N-(3-sulfopropyl)-alkylammonium]ethane (where the carbon number of the alkyl chain is 4, 8, 10, 12, 14, 16, or 18) and p-toluenesulfonic acid monohydrate were synthesized. The catalytic ionic liquids were applied in three-component Mannich reactions with an aldehyde, ketone, and amine at 25 °C in water. The effects of the type and amount of catalyst and reaction time as well as the scope of the reaction were investigated. Results showed that GBAIL-C14 has excellent catalytic activity and fair reusability. The catalytic procedure was simple, and the catalyst could be recycled seven times via a simple separation process without noticeable decreases in catalytic activity. PMID:24837832

He, Leqin; Qin, Shenjun; Chang, Tao; Sun, Yuzhuang; Zhao, Jiquan



Efficient disproportionation of formic acid to methanol using molecular ruthenium catalysts.  


The disproportionation of formic acid to methanol was unveiled in 2013 using iridium catalysts. Although attractive, this transformation suffers from very low yields; methanol was produced in less than 2% yield, because the competitive dehydrogenation of formic acid (to CO2 and H2) is favored. We report herein the efficient and selective conversion of HCOOH to methanol in 50% yield, utilizing ruthenium(II) phosphine complexes under mild conditions. Experimental and theoretical (DFT) results show that different convergent pathways are involved in the production of methanol, depending on the nature of the catalyst. Reaction intermediates have been isolated and fully characterized and the reaction chemistry of the resulting ruthenium complexes has been studied. PMID:25088282

Savourey, Solène; Lefèvre, Guillaume; Berthet, Jean-Claude; Thuéry, Pierre; Genre, Caroline; Cantat, Thibault



Characterization of acidic properties of microporous and mesoporous zeolite catalysts using TGA and DSC  

SciTech Connect

Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied for characterizing the acidic properties of microporous and mesoporous zeolite catalysts through temperature-programmed desorption (TPD) of n-butylamine (n-BA). A flow system was designed with heating and evacuation capability for preparing the n-BA adsorbed sample. The sample was then transferred to TGA (or DSC) apparatus. n-BA desorption conducted on TGA at different temperatures represents the interaction with surface acidic sites of different strength. BAse desorption at 100-240{degrees}C, 240-340{degrees}C, and 340-500{degrees}C, was classified as weak, intramediate, and strong acid sites, respectively. DSC indicates the endothermic nature of the differential thermogravimetric peaks (observed from TGA) in the above temperature regimes, confirming the TPD data. The microporous zeolites examined include three proton-form mordenites, three proton-form and metal-ion exchanged Y-zeolites, and four noble metal catalysts supported on mordenite and Y-zeolite. Four mesoporous zeolites were synthesized and examined by the same TPD method. Both the total acidity (mmol/g) and acid strength distribution depend on the zeolite type. Si/Al ratio, and metal loading. Ni and La ion-exchange decreased the strong acid sites. Pt and Pd loading on an HY decreased the strong acid sites but their loading on an H-mordenite had little effect on its strong acid sites. Mesoporous zeolites showed lower acidity and lower fraction of strong acid sites compared to HY and H-mordenites. However, the acidity of mesoporous zeolites strongly depends on the aluminum source compounds used in the hydrothermal synthesis of the zeolites.

Song, Chunshan; Lai, Wei-Chuan; Schmitz, A.D.; Reddy, K.M. [Pennsylvania State Univ., University Park, PA (United States)] [and others



Ionic Liquids as Catalysts for Sulfuric Acid Production and Cleaning of Flue Gases  

Microsoft Academic Search

\\u000a The present paper is concerned with catalytic pollution abatement of sulfur and nitrogen oxides in flue gases from industrial\\u000a sources. Especially fundamental and applied research on industrial catalysts and their model systems is presented with regards\\u000a to cleaning of flue gases from fossil fuel based power plants and plants producing sulfuric acid. Combined DeSOx and DeNOx processes are very common

Rasmus Fehrmann; K. M. Eriksen; S. B. Rasmussen; J. Winnick


Low equivalent weight short-side-chain perfluorosulfonic acid ionomers in fuel cell cathode catalyst layers  

Microsoft Academic Search

The morphology and fuel cell performance of cathode catalyst layers (CCLs) using low equivalent weight (EW) short-side-chain (SSC) perfluorosulfonic acid ionomers have been investigated in this work. The results were compared with those for a baseline CCL containing 30wt% of the conventional ionomer 1100 EW Nafion®. The CCLs fabricated with 10–20wt% of the Aquivion™ ionomer displayed a similar morphology to

Chao Lei; Dmitri Bessarabov; Siyu Ye; Zhong Xie; Steven Holdcroft; Titichai Navessin




Microsoft Academic Search

Our objective was to compare 1.09 M methanolic HCl to 14% BF3 in methanol as catalysts for direct transesterification of fatty acids in freeze-dried forage samples. Samples included blue grama (Bouteloua gracilis), fringed sage (Artemisia frigida), western wheatgrass (Pascopyrum smithii), needle-and-thread (Stipa comata), dalmation toadflax (Linaria dalmatica), needleleaf sedge (Carex eleocharis), and scarlet globemallow (Sphaelercea coccinea). Thin layer chromatographic evaluation

T. R. Weston; J. D. Derner; C. M. Murrieta; B. W. Hess



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

SciTech Connect

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.

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



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

NASA Astrophysics Data System (ADS)

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.

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



Catalysis Letters 51 (1998) 1522 15 The role of acid sites in cobalt zeolite catalysts for selective  

E-print Network

Catalysis Letters 51 (1998) 15­22 15 The role of acid sites in cobalt zeolite catalysts Received 13 August 1997; accepted 9 January 1998 The role of the acidic support in ion-exchanged cobalt-zeolite acidic zeolites [4,10,15­17], such as ZSM-5 and morden- ite, the role of zeolite remains unclear [3

Regalbuto, John R.


Isotope composition of carbon in amino acids of solid bitumens  

NASA Astrophysics Data System (ADS)

Primary data are presented on the isotope composition of carbon in individual amino acids from solid bitumens and several biological objects. The amino acids of biological objects are characterized by wide variations of the isotope composition of carbon. This fact occurs owing to the difference in biochemical paths of metabolism resulting in the synthesis of individual amino acids. The ?13C values are somewhat decreased for individual amino acids in asphaltenes, varying from -7.7 to -31.7‰. The carbon of amino acids is weighted in kerits from Bad'el' compared to asphaltenes. All the natural bitumens retain the characteristic trend for natural substances: the isotopically heavy and light amino acids by carbon are glycine and leucine, respectively. The isotope composition of amino-acid carbon is lightened compared to natural bitumens in the samples formed under a pronounced thermal impact (asphalt-like crust and kirishite).

Shanina, S. N.; Bushnev, D. A.



Essential role of catalysts (Mn, Au, and Sn) in the vapor liquid solid growth kinematics of ZnS nanowires  

SciTech Connect

In this paper, we demonstrate that surface energy of the catalyst is a vital parameter for the growth rate, self doping of the self assembled nanowires synthesized by employing vapor liquid solid growth technique. The synthesis of ZnS nanowires was done by selectively using three different catalysts (Mn, Au, and Sn), where Au, is the most common catalyst, was used as a reference. The distinctive difference in the growth rate was due to the surface energy of the metal alloy droplet and the interface energies, as explained theoretically using thermodynamic approach. We have found that the activation energy of diffusion of (Zn, S) species in the catalyst droplet was low in Sn (0.41?eV for Zn and 0.13?eV for S) and high in Mn (1.79?eV for Zn and 0.61?eV for S) compared to Au (0.62?eV for Zn and 0.21?eV for S) catalyzed ZnS nanostructures. The thermodynamic calculations predicted the growth rates of Sn (7.5?nm/s) catalyzed nanowires was faster than Au (5.1?nm/s) and Mn (4.6?nm/s) catalyzed ZnS nanostructures, which were in agreement with the experimental results. Finally, the location of the catalyst as dopant in the grown nanostructure was predicted and compared with experimental observations.

Rehman, S.; Shehzad, M. A.; Hafeez, M.; Bhatti, A. S., E-mail: [Center for Micro and Nano Devices (CMND), Department of Physics, COMSATS Institute of Information Technology, Islamabad 44000 (Pakistan)



Essential role of catalysts (Mn, Au, and Sn) in the vapor liquid solid growth kinematics of ZnS nanowires  

NASA Astrophysics Data System (ADS)

In this paper, we demonstrate that surface energy of the catalyst is a vital parameter for the growth rate, self doping of the self assembled nanowires synthesized by employing vapor liquid solid growth technique. The synthesis of ZnS nanowires was done by selectively using three different catalysts (Mn, Au, and Sn), where Au, is the most common catalyst, was used as a reference. The distinctive difference in the growth rate was due to the surface energy of the metal alloy droplet and the interface energies, as explained theoretically using thermodynamic approach. We have found that the activation energy of diffusion of (Zn, S) species in the catalyst droplet was low in Sn (0.41 eV for Zn and 0.13 eV for S) and high in Mn (1.79 eV for Zn and 0.61 eV for S) compared to Au (0.62 eV for Zn and 0.21 eV for S) catalyzed ZnS nanostructures. The thermodynamic calculations predicted the growth rates of Sn (7.5 nm/s) catalyzed nanowires was faster than Au (5.1 nm/s) and Mn (4.6 nm/s) catalyzed ZnS nanostructures, which were in agreement with the experimental results. Finally, the location of the catalyst as dopant in the grown nanostructure was predicted and compared with experimental observations.

Rehman, S.; Shehzad, M. A.; Hafeez, M.; Bhatti, A. S.



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

NASA Astrophysics Data System (ADS)

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.

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



Niobium Complexes As Lewis Acid and Radical Catalysts  

SciTech Connect

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}.

Wayne Tikkanen



Nano scale magnetically recoverable supported heteropoly acid as an efficient catalyst for the synthesis of benzimidazole derivatives in water.  


12-Tungstophosphoric acid supported on silica-coated magnetic nano particles was prepared and characterized by transmission electron microscopy, scanning electron microscopy, powder X-ray diffraction and inductively coupled plasma atomic emission spectroscopy. Acidity of the catalysts was measured by potentiometric titration with n-butylamine. Catalytic activity of the prepared sample was evaluated in the model synthesis of 1,2-disubstituted benzimidazole derivatives in water. The catalyst showed excellent catalytic activity and the corresponding products were obtained in good to excellent yields under mild reaction conditions. Furthermore, the catalyst could be easily recovered using an external magnet and reused several times. The leaching and surface acidity of the recovered catalyst were also investigated. PMID:24664342

Rafiee, Ezzat; Rahpeima, Nasibeh; Eavani, Sara



Characterization of iron counter-ion environment in bulk and supported phosphomolybdic acid based catalysts  

NASA Astrophysics Data System (ADS)

Extended X-ray absorption fine structure (EXAFS) was used to characterize the environment of iron counter-cations in Keggin type phosphomolybdic compounds used as catalysts for oxidation reactions. Iron doped compounds corresponding to bulk acid and to acid supported on the cesium salt were prepared and studied. Iron formed hexa-hydrated complex of both Fe3+ and Fe2+ in the bulk acid, whereas it was present as Fe(OH)2+ hydroxy-cations in the acid supported on the cesium salt. Upon heating the hexa-hydrated complex lost one molecule of water to bind to the Keggin anion through a terminal oxygen. (Fe O Mo bond). The environment of the iron hydroxy-cation changed upon heating while its closer coordination append to remained unchanged.

Huynh, Q.; Millet, J. M. M.



Process optimization and performance evaluation on sequential ionic liquid dissolution-solid acid saccharification of sago waste.  


The production of reducing sugars from sago waste via sequential ionic liquid dissolution-solid acid saccharification was optimized in this study. Ionic liquid dissolution of sago waste with 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was conducted prior to the solid acid saccharification with Amberlyst 15 (A15). The effect of time, temperature and substrate loading during dissolution reaction; and the effect of time, temperature and catalyst loading during saccharification reaction were examined by applying central composite design (CCD) separately. Both dissolution and saccharification reactions were respectively modeled into quadratic polynomial equations with good predictive accuracies. A high reducing sugars yield of 98.3% was obtained under the optimized conditions, i.e. dissolution at 1.75h, 160°C, 1.5% substrate loading, and saccharification at 0.5h, 130°C, 4% catalyst loading. From comparison studies of different saccharification schemes, the sequential ionic liquid dissolution-solid acid saccharification has proven to be a potential method in reducing sugars production from the lignocellulosic biomass. PMID:23280179

Lee, Kiat Moon; Ngoh, Gek Cheng; Chua, Adeline Seak May



Esterification of free fatty acids using water-tolerable Amberlyst as a heterogeneous catalyst.  


To produce biodiesel from high free fatty acid (FFA) oils, the esterification characteristics of two kinds of heterogeneous acid catalysts, Amberlyst 15 and Amberlyst BD20, were compared. When the FFA contents of oils were 50.0 and 99.8 wt%, the activity of Amberlyst 15 gradually decreased with recycling, whereas the activity of Amberlyst BD20 was maintained during recycling. The activity of Amberlyst 15 was inhibited by the water produced during the esterification process, but the activity of Amberlyst BD20 was not similarly affected by water. In images obtained with a scanning electron microscope (SEM), many pores were seen within the Amberlyst 15 catalyst, whereas Amberlyst BD20 showed few pores. Despite the fact that the pores of the catalyst play a role in increasing the number of active sites, Amberlyst BD20, which had fewer pores, was deemed to have more desirable performance in reducing the inhibition by water of the esterification of high FFA oils. PMID:19362818

Park, Ji-Yeon; Kim, Deog-Keun; Lee, Jin-Suk



Stability of solid oxide fuel cell anodes based on YST-SDC composite with Ni catalyst  

NASA Astrophysics Data System (ADS)

Ceramic material based on composite of yttria-doped SrTiO3 (YST) and samaria-doped ceria (SDC) incorporated with Ni catalyst has been evaluated as an anode of solid oxide fuel cell to substitute the use of conventional Ni-based cermets. The results indicated the advantages of suitable Ni addition which could remarkably enhance the electrochemical performance of anode due to the superior in catalytic activity of SDC and Ni towards fuel oxidation. Temperature-programmed reduction (TPR) profiles indicated the existence of bulk-free and interacted NiO in the composites. The cells with Ni/YST-SDC (20 wt% NiO) anodes exhibited stable performance in the prolong operation with tremendously severe conditions in methane fuel with low steam to carbon ratio (S/C = 0.1) and highly humidified hydrogen fuel (40% H2O-H2) compared with the conventional Ni-based cermets. Small amount of deposited carbon was observed and played insignificant effects on the electrochemical performance after the operation for 100 h. The stable performance was ascribable to the excellence in YST-SDC ceramic framework that effectively suppressed the carbon formation. Furthermore, the Ni/YST-SDC anode showed high tolerance in encountering with the redox cycles. From these results, Ni/YST-SDC composite is considered to be a promising candidate for SOFC anode material operating in severe conditions.

Puengjinda, Pramote; Muroyama, Hiroki; Matsui, Toshiaki; Eguchi, Koichi



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

E-print Network

for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures is accurately known. Keggin-type polyoxometalate (POM) clusters and zeolitic solid acids with well

Iglesia, Enrique


Degradation of Fe/N/C catalysts upon high polarization in acid medium.  


A comprehensive study of the degradation of a highly active Fe/N/C catalyst in acid medium is reported. An accelerated aging protocol was applied in the temperature range of 20 to 80 °C. From fundamental rotating-disc electrode studies and polymer electrolyte membrane fuel cell investigations combined with identical-location electron microscopy and Mößbauer spectroscopy at various stages of degradation, important insights into the structural and chemical changes of the catalyst were obtained. Most importantly, the degradation is strongly enhanced at elevated temperature, which is correlated to (i) increased carbon-corrosion rate and (ii) parallel non-preferential dissolution of the FeNx-based active sites. The degradation not only leads to a decreased ORR kinetics over time but also induces significant charge- and mass-transport resistances due to the collapse of the electrode structure. PMID:25070913

Goellner, Vincent; Baldizzone, Claudio; Schuppert, Anna; Sougrati, Moulay Tahar; Mayrhofer, Karl; Jaouen, Frédéric



High-temperature sulfuric acid decomposition over complex metal oxide catalysts  

SciTech Connect

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.

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



Metal amides as the simplest acid/base catalysts for stereoselective carbon-carbon bond-forming reactions.  


In this paper, new possibilities for metal amides are described. Although typical metal amides are recognized as strong stoichiometric bases for deprotonation of inert or less acidic hydrogen atoms, transition-metal amides, namely silver and copper amides, show interesting abilities as one of the simplest acid/base catalysts in stereoselective carbon-carbon bond-forming reactions. PMID:23775980

Yamashita, Yasuhiro; Kobayashi, Sh?



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

SciTech Connect

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.

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



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


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

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



Rhodium Containing Magnetic Nanoparticles: Effective Catalysts for Hydrogenation and the 1,4Addition of Boronic Acids  

Microsoft Academic Search

New efficient rhodium catalysts supported on superparamagnetic iron oxide nanoparticles (NPs) have been prepared using a novel\\u000a method involving sulfonated triphenylphosphine ligands. They successfully promote the hydrogenation of olefins as well as\\u000a the addition of arylboronic acids to dimethyl itaconate (ItMe2) in water for up to 10 recycles. The catalysts were stable towards leaching of the metal complexes and were

Urszula Laska; Christopher G. Frost; Pawel K. Plucinski; Gareth J. Price



Increase of reformate yield by using polyacrylic acid as template in preparation of Pt\\/Re naphtha reforming catalysts  

Microsoft Academic Search

The need for naphtha reforming to produce high quality reformate for gasoline blend stocks with increased yield has become more urgent due to dwindling crude oil reserves and stringent air pollution regulations. Reforming catalysts prepared using polyacrylic acid (PAA) as a metal ion template exhibited 1.4–2.4% improvement in reformate yield and 1.0–2.0wt% lower aromatic production compared to commercially available catalysts

Changkun Liu; Qing Zhu; Zhihua Wu; Zhenhua Zhou; Gaurang Bhargava; Sukesh Parasher; Michael Rueter; Bing Zhou; Jingguang G. Chen



Ring-opening polymerization of lactides catalyzed by natural amino-acid based zinc catalysts.  


A series of chiral NNO-tridentate Schiff base ligands derived from natural amino acids were reacted with zinc(bis-trimethylsilylamide)(2) to provide metal complexes which have been fully characterized. One of these derivatives was further reacted with p-fluorophenol to yield a phenoxide complex. X-ray crystallographic studies reveal the zinc Schiff base amide complexes to be monomeric, whereas, the p-fluorophenolate complex was shown to be dimeric with bridging phenoxide ligands. All zinc complexes were shown to be very effective catalysts for the ring-opening polymerization (ROP) of lactides at ambient temperature, producing polymers with controlled and narrow molecular weight distributions. These enantiomerically pure zinc complexes did not show selectivity toward either L- or D-lactide, that is, k(D(obsd))/k(L(obsd)) approximately = 1. However, steric substituents on the Schiff base ligands exhibited moderate to excellent stereocontrol for the ROP of rac-lactide. Heterotactic polylactides were produced from rac-lactide with P(r) values ranging from 0.68 to 0.89, depending on the catalyst employed and the reaction temperature. The reactivities of the various catalysts were greatly affected by substituents on the Schiff base ligands, with sterically bulky substituents being rate enhancing. PMID:20121063

Darensbourg, Donald J; Karroonnirun, Osit



Efficient cluster-based catalysts for asymmetric hydrogenation of ?-unsaturated carboxylic acids.  


The new clusters [H(4)Ru(4)(CO)(10)(?-1,2-P-P)], [H(4)Ru(4)(CO)(10) (1,1-P-P)] and [H(4)Ru(4)(CO)(11)(P-P)] (P-P=chiral diphosphine of the ferrocene-based Josiphos or Walphos ligand families) have been synthesised and characterised. The crystal and molecular structures of eleven clusters reveal that the coordination modes of the diphosphine in the [H(4)Ru(4)(CO)(10)(?-1,2-P-P)] clusters are different for the Josiphos and the Walphos ligands. The Josiphos ligands bridge a metal-metal bond of the ruthenium tetrahedron in the "conventional" manner, that is, with both phosphine moieties coordinated in equatorial positions relative to a triangular face of the tetrahedron, whereas the phosphine moieties of the Walphos ligands coordinate in one axial and one equatorial position. The differences in the ligand size and the coordination mode between the two types of ligands appear to be reflected in a relative propensity for isomerisation; in solution, the [H(4)Ru(4)(CO)(10)(1,1-Walphos)] clusters isomerise to the corresponding [H(4)Ru(4)(CO)(10)(?-1,2-Walphos)] clusters, whereas the Josiphos-containing clusters show no tendency to isomerisation in solution. The clusters have been tested as catalysts for asymmetric hydrogenation of four prochiral ?-unsaturated carboxylic acids and the prochiral methyl ester (E)-methyl 2-methylbut-2-enoate. High conversion rates (>94%) and selectivities of product formation were observed for almost all catalysts/catalyst precursors. The observed enantioselectivities were low or nonexistent for the Josiphos-containing clusters and catalyst (cluster) recovery was low, suggesting that cluster fragmentation takes place. On the other hand, excellent conversion rates (99-100%), product selectivities (99-100% in most cases) and good enantioselectivities, reaching 90% enantiomeric excess (ee) in certain cases, were observed for the Walphos-containing clusters, and the clusters could be recovered in good yield after completed catalysis. Results from high-pressure NMR and IR studies, catalyst poisoning tests and comparison of catalytic properties of two [H(4)Ru(4)(CO)(10)(?-1,2-P-P)] clusters (P-P=Walphos ligands) with the analogous mononuclear catalysts [Ru(P-P)(carboxylato)(2)] suggest that these clusters may be the active catalytic species, or direct precursors of an active catalytic cluster species. PMID:22890820

Moberg, Viktor; Duquesne, Robin; Contaldi, Simone; Röhrs, Oliver; Nachtigall, Jonny; Damoense, Llewellyn; Hutton, Alan T; Green, Michael; Monari, Magda; Santelia, Daniela; Haukka, Matti; Nordlander, Ebbe



Methanetrisulfonic Acid: A Highly Efficient Strongly Acidic Catalyst for Wagner-Meerwein Rearrangement, Friedel-Crafts Alkylation and Acylation Reactions. Examples from Vitamin E Synthesis  

Microsoft Academic Search

Methanetrisulfonic acid had been prepared for the first time over 140 years ago, but it was used only scarcely in chemical transformations. In the course of our activities dealing with key-steps of industrial syntheses of vitamins, e.g. economically important vitamin E (acetate), we found that methanetrisulfonic acid is an extremely effective catalyst in a variety of reactions. Examples of its

Werner Bonrath; Fabrice Aquino; Alois Haas; Simone Hoppmann; Thomas Netscher; Francesco Pace; Horst Pauling



Solid phase sequencing of double-stranded nucleic acids  


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.

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



Enhanced performance of the catalytic conversion of allyl alcohol to 3-hydroxypropionic acid using bimetallic gold catalysts.  


One of the strategic building blocks in organic synthesis is 3-hydroxypropionic acid, which is particularly important for the manufacture of high performance polymers. However, to date, despite many attempts using both biological and chemical routes, no large scale effective process for manufacturing 3-hydroxypropionic acid has been developed. One potentially useful starting point is from allyl alcohol, as this can be obtained in principle from the dehydration of glycerol, thereby presenting a bio-renewable green pathway to this important building block. The catalytic transformation of allyl alcohol to 3-hydroxypropionic acid presents interesting challenges in catalyst design, particularly with respect to the control of selectivity among the products that can be expected, as acrylic acid, acrolein and glyceric acid can also be formed. In this paper, we present a novel eco-sustainable catalytic pathway leading to 3-hydroxypropionic acid, which highlights the outstanding potential of gold-based and bimetallic catalysts in the aerobic oxidation of allyl alcohol. PMID:22455056

Falletta, Ermelinda; Della Pina, Cristina; Rossi, Michele; He, Qian; Kiely, Christopher J; Hutchings, Graham J



Selective catalytic production of 5-hydroxymethylfurfural from glucose by adjusting catalyst wettability.  


The development of highly-efficient catalysts for conversion of glucose and fructose to 5-hydroxymethylfurfural (HMF) is of great importance. In this work, theoretical simulations form the basis for rational design and synthesis of a superhydrophobic mesoporous acid, that can completely prevent HMF hydration, giving HMF as sole product from full conversion of fructose. Interestingly, the combined superhydrophobic solid acid and superhydrophilic solid base catalysts are very efficient for one-pot conversion of glucose to HMF, giving a yield as high as 95.4 %. The excellent catalytic data in the conversion of glucose to HMF is attributed to the unique wettabilities of the solid acid and base catalysts. PMID:24399510

Wang, Liang; Wang, Hong; Liu, Fujian; Zheng, Anmin; Zhang, Jian; Sun, Qi; Lewis, James P; Zhu, Longfeng; Meng, Xiangju; Xiao, Feng-Shou



Liquid Hydrofluoric Acid Sorption Using Solid Media - Part 1  

Microsoft Academic Search

The conversion of the uranium hexafluoride (UFâ) which is removed from the Molten Salt Reactor Experiment (MSRE), into a stable oxide for long-term storage will produce a significant amount of slightly contaminated, concentrated aqueous hydrofluoric acid (HF). Sin&the handling of this HF is complicated and dangerous, it was decided to transform it into a stable solid fluoride (e.g., CaFâ, AlFâ,




Catalytic pyrolysis of oil fractions separated from food waste leachate over nanoporous acid catalysts.  


Oil fractions, separated from food waste leachate, can be used as an energy source. Especially, high quality oil can be obtained by catalytic cracking. In this study, nanoporous catalysts such as Al-MCM-41 and mesoporous MFI type zeolite were applied to the catalytic cracking of oil fractions using the pyrolysis gas chromatography/mass spectrometry. Mesoporous MFI type zeolite showed better textural porosity than Al-MCM-41. In addition, mesoporous MFI type zeolite had strong Brönsted acidity while Al-MCM-41 had weak acidity. Significant amount of acid components in the food waste oil fractions were converted to mainly oxygenates and aromatics. As a result of its well-defined nanopores and strong acidity, the use of a mesoporous MFI type zeolite produced large amounts of gaseous and aromatic compounds. High yields of hydrocarbons within the gasoline range were also obtained in the case of mesoporous MFI type zeolite, whereas the use of Al-MCM-41, which exhibits relatively weak acidity, resulted in high yields of oxygenates and diesel range hydrocarbons. PMID:22121679

Kim, Seung-Soo; Heo, Hyeon Su; Kim, Sang Guk; Ryoo, Ryong; Kim, Jeongnam; Jeon, Jong-Ki; Park, Sung Hoon; Park, Young-Kwon



Solar active fire clay based hetero-Fenton catalyst over a wide pH range for degradation of Acid Violet 7.  


Fe(III) immobilized fire clay (Fe-FC) was prepared using ferric nitrate by solid state dispersion method and this hetero-Fenton catalyst was applied for the degradation of Acid Violet 7 (AV 7) under natural sunlight. The 26% ferric nitrate loaded fire clay was found to be most efficient. The experimental conditions such as solution pH, H2O2 concentration for efficient degradation of AV 7 have been determined. Unlike Fenton catalyst, Fe-FC is photoactive over a wide pH range of 3-7. This catalyst was found to be stable and reusable. The GC-MS analysis of experimental solutions during irradiation revealed the formation of 2,8-diaminonaphthalene-1,3,6-triol, 8-aminonaphthalene-1,2,3,6-tetrol, 2-aminonaphthalene-1,3,6,8-tetrol and 2-aminobenzene-1,3-diol/5-aminonbenzene-1,3-diol/ 2-aminobenzene-1,4-diol as intermediates. The 26% ferric nitrate loaded fire clay was characterized by XRD, ICP-AES, BET surface area, FT-IR, SEM-EDS and UV-DRS studies. PMID:22655369

Muthuvel, Inbasekaran; Krishnakumar, Balu; Swaminathan, Meenakshisundaram



Photodissociation of Formic Acid Isolated in Solid Parahydrogen  

NASA Astrophysics Data System (ADS)

The in situ photochemistry of dopant molecules isolated in solid parahydrogen (pH_2) typically differs from analogous studies in rare gas crystals for two main reasons: (1) solid pH_2 has a negligible cage effect so that photodissociation of a precursor molecule can lead efficiently to well-separated fragments, and (2) radical fragments can potentially react with the pH_2 matrix. Our group is currently studying the 193 nm photochemistry of a number of precursor molecules isolated in solid pH_2 via high-resolution FTIR spectroscopy. In this talk I will present results for the 193 nm photolysis of formic acid (FA) in solid pH_2. In rare gas matrices, the analogous FA photochemistry proceeds via the CO+H_2O and CO_2+H_2 photodissociation channels. In solid pH_2, in addition to these channels we observe the production of HCO and HOCO. Further, after the UV laser is turned off, the HOCO concentration continues to increase with a slow first-order rate constant for a period of 10 hours. At this point, we still do not have a full explanation of the chemical mechanism leading to the post-photolysis increase in the HOCO concentration. J. Lundell, M. Räsänen, J. Mol. Struct. 436-437, 349 (1997).

Anderson, David T.; Paulson, Leif O.



Three-phase catalytic system of H2O, ionic liquid, and VOPO4-SiO2 solid acid for conversion of fructose to 5-hydroxymethylfurfural.  


Efficient transformation of biomass-derived feedstocks to chemicals and fuels remains a daunting challenge in utilizing biomass as alternatives to fossil resources. A three-phase catalytic system, consisting of an aqueous phase, a hydrophobic ionic-liquid phase, and a solid-acid catalyst phase of nanostructured vanadium phosphate and mesostructured cellular foam (VPO-MCF), is developed for efficient conversion of biomass-derived fructose to 5-hydroxymethylfurfural (HMF). HMF is a promising, versatile building block for production of value-added chemicals and transportation fuels. The essence of this three-phase system lies in enabling the isolation of the solid-acid catalyst from the aqueous phase and regulation of its local environment by using a hydrophobic ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]). This system significantly inhibits the side reactions of HMF with H2O and leads to 91?mol?% selectivity to HMF at 89?% of fructose conversion. The unique three-phase catalytic system opens up an alternative avenue for making solid-acid catalyst systems with controlled and locally regulated microenvironment near catalytically active sites by using a hydrophobic ionic liquid. PMID:24729382

Tian, Chengcheng; Zhu, Xiang; Chai, Song-Hai; Wu, Zili; Binder, Andrew; Brown, Suree; Li, Lin; Luo, Huimin; Guo, Yanglong; Dai, Sheng



Amino acid derived Cu(II) compounds as catalysts for asymmetric oxidative coupling of 2-naphthol.  


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

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



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

SciTech Connect

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.

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



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

NASA Astrophysics Data System (ADS)

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.

Adijanto, Lawrence


Cyclization of alkynoic acids in water in the presence of a vesicular self-assembled amphiphilic pincer palladium complex catalyst.  


Alkynoic acids were cyclized in the presence of a vesicular palladium-based catalyst and a catalytic amount of triethylamine in water to give the corresponding lactones in moderate-to-good yields. The formation of a vesicular structure was shown to be essential for the promotion of the reaction. PMID:25303771

Hamasaka, Go; Uozumi, Yasuhiro



Graphene nanosheets-polypyrrole hybrid material as a highly active catalyst support for formic acid electro-oxidation  

E-print Network

Graphene nanosheets-polypyrrole hybrid material as a highly active catalyst support for formic acid. Therefore, the synthesis of hybrid materials consisting of reduced graphene oxide (RGO) with PPy matrix A novel electrode material based on graphene oxide (GO)-polypyrrole (PPy) composites was synthesized

Gao, Hongjun


Pt\\/TiO 2 (rutile) catalysts for sulfuric acid decomposition in sulfur-based thermochemical water-splitting cycles  

Microsoft Academic Search

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 1wt% Pt\\/TiO2 (rutile) catalysts submitted to flowing concentrated sulfuric acid at 1123K and atmospheric pressure for different times

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



SO?H-functionalized acidic ionic liquids as catalysts for the hydrolysis of cellulose.  


The conversion of cellulose into valuable chemicals to deal with the depletion of fossil fuel has got much attention. Completing the hydrolysis of cellulose under mild conditions is the key step. In this study, six kinds of SO(3)H-functionalized acidic ionic liquids were used as acid catalyst to promote the hydrolysis of cellulose in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl). All of them were efficient for the hydrolysis of cellulose, with the maximum total reducing sugars (TRS) yields over 83% at 100 °C. Acidic ionic liquids with analogous structures showed similar catalytic activities. Triethyl-(3-sulfo-propyl)-ammonium hydrogen sulfate (IL-5 in this study) was the optimum ionic liquid for cellulose hydrolysis, with the maximum TRS yield at 100 °C up to 99% when the dosage used was 0.2g. In addition, the water in [BMIM]Cl had negative effect on cellulose hydrolysis. Therefore, controlling the content of water in a comparatively low level is quite necessary. PMID:23218286

Liu, Yuanyuan; Xiao, Wenwen; Xia, Shuqian; Ma, Peisheng



The Role of the Liquid?Solid Interface in the Preparation of Supported Catalysts  

Microsoft Academic Search

The contribution of the Interface Science to the preparation of supported catalysts during the last two decades is presented. It is illustrated how the concepts and the methodologies of the Interface Science could be effectively used for an in?depth understanding of the phenomena involved in the initial preparation step. This, extremely critical step, concerns the deposition of transition metal species

Kyriakos Bourikas; Christos Kordulis; Alexis Lycourghiotis



On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts  

E-print Network

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 ...

Wang, Lee-Ping


Solid-state forms of zoledronic acid: polymorphism in hydrates.  


Solid-state forms of zoledronic acid, a nitrogen-containing bisphosphonate used for treatment of bone diseases are studied using different experimental techniques (DSC, TG, and XRD). Two degrees of hydration have been obtained, containing one and three water molecules per zoledronic acid molecule. The crystal structure of the trihydrated form is reported. Two different anhydrated forms have been obtained when the hydrated ones were heated. Besides, during the dehydration process, an amount of metastable amorphous phase appears, as a function of the dehydration rate. The stability of the obtained crystalline forms is examined under high humidity and a different trihydrated form was obtained, setting clear that the same degree of hydration (trihydrated) can be obtained in two different crystalline forms, and then very different thermal behaviors have been observed. PMID:20533554

Ruscica, Romina; Bianchi, Micaela; Quintero, Mariano; Martinez, Andrea; Vega, Daniel R



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

SciTech Connect

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.

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



Characterization of Lewis acidity of cation-exchanged montmorillonite K-10 clay as effective heterogeneous catalyst for acetylation of alcohol  

Microsoft Academic Search

Catalytic activity of 14 types of metal ion-exchanged montmorillonite K-10 clay (Mn+-mont) is tested for the acetylation of cyclohexanol with acetic anhydride at room temperature. The activity increases with an increase in the charge\\/radius ratio of exchanged cation. The activity of Fe3+-mont is the highest and is higher than those of other Fe3+ catalysts, FeCl3·6H2O and FeCl3\\/SiO2, conventional acid catalysts,

Ken-ichi Shimizu; Tomoya Higuchi; Emi Takasugi; Tsuyoshi Hatamachi; Tatsuya Kodama; Atsushi Satsuma



Low-grade oils and fats: effect of several impurities on biodiesel production over sulfonic acid heterogeneous catalysts.  


Different lipidic wastes and low-grade oils and fats have been characterized and evaluated as feedstocks for the acid-catalyzed production of FAME. The characterization of these materials has revealed significant contents of free fatty acids, Na, K, Ca, Mg, P, unsaponifiable matter and humidity. Arenesulfonic acid-functionalized SBA-15 silica catalyst has provided yields to FAME close to 80% in the simultaneous esterification-transesterification of the different feedstocks, regardless of their nature and properties, using methanol under the following reaction conditions: 160 °C, 2 h, methanol to oil molar ratio of 30, 8 wt.% catalyst loading, and 2000 rpm stirring rate. Nevertheless, reutilization of the catalyst is compromised by high levels of impurities, especially because of deactivation by strong interaction of unsaponifiable matter with the catalytic sites. The conditioning of these materials by aqueous washing in the presence of cationic-exchange resin Amberlyst-15, followed by a drying step, resulted in a lower deactivation of the catalyst. PMID:21862322

Morales, Gabriel; Bautista, L Fernando; Melero, Juan A; Iglesias, Jose; Sánchez-Vázquez, Rebeca



Palladium(0) nanoclusters stabilized by poly(4-styrenesulfonic acid-co-maleic acid) as an effective catalyst for Suzuki–Miyaura cross-coupling reactions in water  

Microsoft Academic Search

Palladium(0) nanoclusters stabilized by poly(4-styrenesulfonic acid-co-maleic acid), PSSA-co-MA, were generated in situ during the hydrolysis of ammonia–borane (AB) from the reduction of potassium tetrachloropalladate(II) in aqueous solution at room temperature. They were isolated from the reaction solution and characterized by UV–visible electronic absorption spectroscopy, TEM, SAED and XRD techniques. The PSSA-co-MA stabilized palladium(0) nanoclusters were used as catalyst in Suzuki–Miyaura

Önder Metin; Feyyaz Durap; Murat Aydemir; Saim Özkar



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


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

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



Influence of the starting aluminum salt on the surface and acid properties of AlPOâ catalysts precipitated with ammonium hydroxide  

Microsoft Academic Search

In this paper, the influence of the starting aluminum salt (chloride, nitrate, or sulfate) and the pretreatment temperature (773-1273 K) on textural properties, crystal structure, and surface acidity of AlPOâ (Al\\/P = 1) catalysts was studied in order to learn how preparation conditions affect catalyst activity in organocationic reactions. The catalysts were characterized using nitrogen adsorption, X-ray diffraction, infrared spectroscopy,

J. M. Campelo; A. Garcia; D. Luna; J. M. Marinas



Catalyst-free fatty acid methyl ester production from wet activated sludge under subcritical water and methanol condition.  


Wet activated sludge was converted directly into biodiesel using water as hydrolysis reagent to enhance the extraction of lipid in activated sludge, and as catalyst for the conversion of neutral lipids into biodiesel under subcritical conditions. At 175°C, 3.5MPa, a methanol to sludge ratio of 30 (mL/g) and a sludge water content of 84wt.%, about 90% conversion to fatty acid methyl esters was achieved within 24h without the need for conventional catalysts such as KOH and H(2)SO(4). Since water is employed as a catalyst, its removal is not required; therefore, the processing costs for producing biodiesel from activated sludge are reduced. The method has the potential for applications to other feedstock with high water contents such as micro-algae. PMID:22940307

Huynh, Lien Huong; Tran Nguyen, Phuong Lan; Ho, Quoc Phong; Ju, Yi-Hsu



Brown algae hydrolysis in 1-n-butyl-3-methylimidazolium chloride with mineral acid catalyst system.  


The amenability of three brown algal species, Sargassum fulvellum, Laminaria japonica and Undaria pinnatifida, to hydrolysis were investigated using the ionic liquid (IL), 1-n-butyl-3-methylimidazolium chloride ([BMIM]Cl). Compositional analyses of the brown algae reveal that sufficient amounts of sugars (15.5-29.4 wt.%) can be recovered. Results from hydrolysis experiments show that careful selection of the type of mineral acid as catalyst and control of acid loading could maximize the recovery of sugars. Optimal reaction time and temperature were determined from the kinetic studies on the sequential reducing sugar (TRS) formation and degradation. Optimal reaction times were determined based on the extent of furfurals formation as TRS degradation products. X-ray diffraction and environmental scanning electron microscopy confirmed the suitability of [BMIM]Cl as solvent for the hydrolysis of the three brown algae. Overall results show the potential of brown algae as renewable energy resources for the production of valuable chemicals and biofuels. PMID:22721878

Malihan, Lenny B; Nisola, Grace M; Chung, Wook-Jin



Ultrasonic enhance acid hydrolysis selectivity of cellulose with HCl-FeCl3 as catalyst.  


The effect of ultrasonic pretreatment coupled with HCl-FeCl3 catalyst was evaluated to hydrolyze cellulose amorphous regions. The ultrasonic pretreatment leads to cavitation that affects the morphology and microstructure of fibers, enhancing the accessibility of chemical reagent to the loosened amorphous regions of cellulose. In this work, Fourier transform infrared spectroscopy (FTIR) was used to identify characteristic absorption bands of the constituents and the crystallinity was evaluated by the X-ray diffraction (XRD) technique. The results indicated that appropriate ultrasonic pretreatment assisted with FeCl3 can enhance the acid hydrolysis of amorphous regions of cellulose, thus improving the crystallinity of the remaining hydrocellulose. It was observed that sonication samples that were pretreated for 300W and 20min followed by acid hydrolysis had maximum of 78.9% crystallinity. The crystallinity was 9.2% higher than samples that were not subjected to ultrasound. In addition, the average fines length decreased from 49?m to 37?m. PMID:25498717

Li, Jinbao; Zhang, Xiangrong; Zhang, Meiyun; Xiu, Huijuan; He, Hang



Heterogenization of Homogeneous Catalysts: the Effect of the Support  

SciTech Connect

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.

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



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

SciTech Connect

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.

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



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

SciTech Connect

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.

Shaw, Wendy J.



MIL-101-SO3H: a highly efficient Brønsted acid catalyst for heterogeneous alcoholysis of epoxides under ambient conditions.  


For the first time, a ?100% sulfonic acid functionalized metal-organic framework (MOF), MIL-101-SO3H, with giant pores has been prepared by a hydrothermal process followed by a facile postsynthetic HCl treatment strategy. The replete readily accessible Lewis acidic and especially Brønsted acidic sites distributed throughout the framework as well as high stability endow the resultant MOF exceptionally high efficiency and recyclability, which surpass all other MOF-based catalysts, for the ring opening of epoxides with alcohols (especially, methanol) as nucleophiles under ambient conditions. PMID:25291973

Zhou, Yu-Xiao; Chen, Yu-Zhen; Hu, Yingli; Huang, Gang; Yu, Shu-Hong; Jiang, Hai-Long



The use of solid state nuclear magnetic resonance (NMR) to study the effect of composition on the properties of equilibrium fluid cracking catalysts (FCCs)  

Microsoft Academic Search

Solid state nuclear magnetic resonance (NMR) spectroscopy together with microactivity testing have been used to characterize the changes that occur in a fluid cracking catalyst (FCC) during gas oil cracking in a refinery fluid catalytic cracking unit (FCCU). The 29Si NMR spectra of fresh FCCs show the well known five peaks pattern attributed to the presence of HY-type crystals. However,

M. L Occelli; U Voigt; H Eckert



Continuous Isosorbide Production From Sorbitol Using Solid Acid Catalysis  

SciTech Connect

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.

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



Stability and spinodal decomposition of the solid-solution phase in the ruthenium-cerium-oxide electro-catalyst.  


The phase diagram of Ru-Ce-O was calculated by a combination of ab initio density functional theory and thermodynamic calculations. The phase diagram indicates that the solubility between ruthenium oxide and cerium oxide is very low at temperatures below 1100 K. Solid solution phases, if existing under normal experimental conditions, are metastable and subject to a quasi-spinodal decomposition to form a mixture of a Ru-rich rutile oxide phase and a Ce-rich fluorite oxide phase. To study the spinodal decomposition of Ru-Ce-O, Ru0.6Ce0.4O2 samples were prepared at 280 °C and 450 °C. XRD and in situ TEM characterization provide proof of the quasi-spinodal decomposition of Ru0.6Ce0.4O2. The present study provides a fundamental reference for the phase design of the Ru-Ce-O electro-catalyst. PMID:25418197

Li, Yanmei; Wang, Xin; Shao, Yanqun; Tang, Dian; Wu, Bo; Tang, Zhongzhi; Lin, Wei



Oxyhydrochlorination catalyst  


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.

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



Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics  

SciTech Connect

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.

Kamil Klier; Richard G. Herman



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

PubMed Central

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




All-solid-state potentiometric sensors for ascorbic acid by using a screen-printed compatible solid contact  

Microsoft Academic Search

The development of all-solid-state potentiometric ion selective electrodes for monitoring of ascorbic acid, by using a screen-printed compatible solid contact is described. The applied methodology is based on the use of PVC membrane modified with some firstly-tested ionophores (triphenyltin(IV)chloride, triphenyltin(IV)hydroxide and palmitoyl-l-ascorbic acid) and a novel one synthesized in our laboratory (dibutyltin(IV) diascorbate). Synthesis protocol and some preliminary identification studies

Panayotis G. Veltsistas; Mamas I. Prodromidis; Constantinos E. Efstathiou



Versatile and sustainable synthesis of cyclic imides from dicarboxylic acids and amines by Nb2O5 as a base-tolerant heterogeneous Lewis acid catalyst.  


Catalytic condensation of dicarboxylics acid and amines without excess amount of activating reagents is the most atom-efficient but unprecedented synthetic method of cyclic imides. Here we present the first general catalytic method, proceeding selectively and efficiently in the presence of a commercial Nb2 O5 as a reusable and base-tolerant heterogeneous Lewis acid catalyst. The method is effective for the direct synthesis of pharmaceutically or industrially important cyclic imides, such as phensuximide, N-hydroxyphthalimide (NHPI), and unsubstituted cyclic imides from dicarboxylic acid or anhydrides with amines, hydroxylamine, or ammonia. PMID:25225033

Ali, Md Ayub; Siddiki, S M A Hakim; Kon, Kenichi; Hasegawa, Junya; Shimizu, Ken-Ichi



Deactivation and acidity deterioration of a SiO[sub 2]/Al[sub 2]O[sub 3] catalyst in the isomerization of cis-butene  

SciTech Connect

The evolution of acidity of a SiO[sub 2]/Al[sub 2]O[sub 3] catalyst in the isomerization of cis-butene has been studied. The catalyst deactivation takes place by blockage of active sites by slightly evolved coke, which is partially soluble in dichloromethane and pyridine and is slightly aromatic. The blockage of active sites has no incidence on the porous structure and on the catalyst surface area. By combining the results for the catalyst in different deactivation states, corresponding to calorimetric and thermogravimetric measurements of tert-butylamine desorption at a programmed temperature, the evolution of the average value of acidity strength has been determined. In addition, from tert-butylamine adsorption measurements at 200C, the evolution of surface acidity strength distribution has been attained. The fast deactivation of very strong acidic sites is concluded.

Gayubo, A.G.; Arandes, J.M.; Aguayo, A.T.; Olazar, M.; Bilbao, J. (Univ. del Pais Vasco, Bilbao (Spain))



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


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.

Aines, Roger D.



Novel catalyst-support interaction for direct formic acid fuel cell anodes: Pd electrodeposition on surface-modified graphite felt  

Microsoft Academic Search

The electrodeposition of Pd on graphite felt (GF, thickness ~3 mm in uncompressed state) was studied and the resulting catalyst\\u000a was compared with Pt-Ru\\/GF for the electro-oxidation of formic acid. A micellar solution composed of the non-ionic surfactant\\u000a Triton X-102 and an aqueous phase containing PdCl2 were utilized for the galvanostatic electrodeposition of Pd nanoparticles. The presence of the surfactant during

Tommy T. Cheng; El?d L. Gyenge



A Simple, Efficient Synthesis of 2-Aryl Benzimidazoles Using Silica Supported Periodic Acid Catalyst and Evaluation of Anticancer Activity  

PubMed Central

A new, efficient method for the synthesis of 2-aryl substituted benzimidazole by using silica supported periodic acid (H5IO6-SiO2) as a catalyst has been developed. The salient feature of the present method includes mild reaction condition, short reaction time, high yield and easy workup procedure. The synthesized benzimidazoles exhibited potent anticancer activity against MCF7 and HL60 cell lines. PMID:24052861

Sontakke, Vyankat A.; Ghosh, Sougata; Lawande, Pravin P.; Chopade, Balu A.; Shinde, Vaishali S.



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


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

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



Sulfonic Acid Functionalized Nano-?-Al2O3: A New, Efficient, and Reusable Catalyst for Synthesis of 3-Substituted-2H-1,4-Benzothiazines  

PubMed Central

A simple and efficient synthetic protocol has been developed for the synthesis of 3-substituted-2H-1,4-benzothiazines by using a novel sulfonic acid functionalized nano-?-Al2O3 catalyst, devoid of corrosive acidic, and basic reagents. The developed method has the advantages of good to excellent yields, short reaction times, operational simplicity, and a recyclable catalyst. The catalyst can be prepared by a simple procedure from inexpensive and readily available nano-?-Al2O3 and has been shown to be recoverable and reusable up to six cycles without any loss of activity. PMID:23935435

Li, Wei Lin; Tian, Shuan Bao; Zhu, Feng



Thin-Membrane Solid-Acid Fuel Cell Tetsuya Uda* and Sossina M. Haile*,z  

E-print Network

of fossil fuels, fuel cells have emerged as attractive alternatives to combustion engines. In additionThin-Membrane Solid-Acid Fuel Cell Tetsuya Uda* and Sossina M. Haile*,z Department of Materials Science, California Institute of Technology, Pasadena, California 91125, USA Solid-acid fuel cells SCFCs


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

SciTech Connect

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.

Yu Xiaofang [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Yu Xiaobo [China Pharmaceutical University, Nanjing 210009 (China); Wu Shujie; Liu Bo; Liu Heng [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Guan Jingqi, E-mail: [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Kan Qiubin, E-mail: [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China)



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


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

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



Rheology of Dilute Acid Hydrolyzed Corn Stover at High Solids Concentration  

Microsoft Academic Search

The rheological properties of acid hydrolyzed corn stover at high solids concentration (20–35 wt.%) were investigated using\\u000a torque rheometry. These materials are yield stress fluids whose rheological properties can be well represented by the Bingham\\u000a model. Yield stresses increase with increasing solids concentration and decrease with increasing hydrolysis reaction temperature,\\u000a acid concentration, and rheometer temperature. Plastic viscosities increase with increasing solids

M. R. Ehrhardt; T. O. Monz; T. W. Root; R. K. Connelly; C. T. Scott; D. J. Klingenberg



Hydrocarbon conversion with hot and cooled regenerated catalyst in series  

SciTech Connect

This patent describes a heat balanced hydrocarbon conversion process wherein a hydrocarbon feed is converted to lower boiling products in a reactor by contacting the same at elevated temperatures with hot fluid cracking catalyst comprising a zeolite containing acid sites to form the lower boiling products. The resulting spent cracking catalyst containing coke from the reactor is separated from reaction products and stripped of volatile hydrocarbons in a stripping zone to provide stripped solid fluid cracking catalyst and the stripped catalyst is regenerated with an oxygen-containing gas in a regeneration zone to provide hot freshly regenerated fluid cracking catalyst which is returned to the reactor. The improvement comprises cooling a portion of the hot freshly regenerated fluid cracking catalyst to provide a cooled portion of regenerated fluid cracking catalyst, and a hot portion of regenerated fluid cracking catalyst, and contacting the cooled portion of regenerated fluid cracking catalyst with the hydrocarbon feed in the reactor downstream of contacting the hydrocarbon feed in the reactor with the hot portion of regenerated fluid cracking catalyst, thereby increasing the ratio of fluid cracking catalyst to the hydrocarbon feed.

Bartholic, D.B.; Barger, D.F.



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

PubMed Central

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

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



On the equilibrium nature of thermodesorption processes. TPD-NH3 studies of surface acidity of Ni/MgO-Al2O3 catalysts.  


This article deals with a quantitative analysis of thermodesorption spectra of ammonia: a technique commonly applied to study the surface acidity of solids. The method used for determination of adsorption energy distributions of ammonia is the same as that published recently for the case of hydrogen thermodesorption (Panczyk, T.; et al. Langmuir 2005, 21, 7311). The developed theoretical expression describing the thermodesorption process is based on the statistical rate theory (SRT) and its analysis leads to the conclusion that majority of thermodesorption processes, carried out under flow conditions, are in fact quasi-equilibrium ones. Similar conclusion has already been drawn by some authors applying the classical absolute rate theory (ART) for analysis of thermodesorption data. This conclusion has important practical consequences. Namely, it greatly simplifies the quantitative analysis of thermodesorption processes since there is no need to use any kinetic approaches to that purpose. The quantitative analysis of thermodesorption spectra can thus be based on commonly accepted relations following from equilibrium thermodynamics. It is worth noting that in quasiequilibrium conditions either the SRT or the ART lead to this same expression with only a slightly different meaning of some constants. Thus, in quasiequilibrium conditions there is no need to decide which theoretical approach should be applied. As an illustration, the ammonia thermodesorption spectra from the modified nickel catalysts are analyzed. The catalysts were prepared by the coprecipitation method and differ by the amount of MgO and NiO, whereas the amount of Al(2)O(3) is constant and equals 30%. It was stated that the presence of MgO reduces the number of acid centers corresponding to high values of ammonia adsorption energy. PMID:16831004

Panczyk, Tomasz; Gac, Wojciech; Panczyk, Monika; Borowiecki, Tadeusz; Rudzinski, Wladyslaw



Base adsorption calorimetry for characterising surface acidity: a comparison between pulse flow and conventional “static” techniques  

Microsoft Academic Search

A pulsed flow adsorption microcalorimeter (pulse-FMC) has been developed by modifying a Setaram 111. It is tested in comparison with a conventional pulsed static adsorption microcalorimeter (pulse-SMC) for characterising surface acidity of solid acid catalysts. Small pulses of 1% ammonia in helium are delivered to an activated catalyst sample and its surface acidity is differentially profiled in terms of the

S. P. Felix; C. Savill-Jowitt; D. R. Brown



Multistage fcc catalyst stripping  

SciTech Connect

This patent describes a fluid catalytic cracking process for cracking hydrocarbons. It comprises: cofeeding active hot solid zeolite cracking catalyst and crackable hydrocarbon feed to a cracking zone; cracking the feed to hydrocarbon products while depositing coke on the catalyst to evolve spent catalyst; disengaging the spent catalyst from the hydrocarbon products; flowing the spent catalyst to a regeneration zone; passing an oxygen-containing gas upwardly through the regeneration zone at sufficient velocity to fluidize the catalyst contained within the regeneration zone; retaining the catalyst in the regeneration zone at elevated temperature for a time sufficient to effect exothermic oxidative regeneration of the catalyst by burning the coke deposited thereon, thereby heating and reactivating the catalyst; providing a catalyst stripping zone comprising three superimposed stages, the stages comprising an upper mixing stage, a central dehydrogenation/stripping stage, and a lower steam stripping stage; mixing spent catalyst with regenerated catalyst in the upper mixing stage of the catalyst stripping zone; retaining the mixture within the upper mixing stage at elevated temperature for a period of time sufficient to effect desorption of cracked products from the spent catalyst; flowing the catalyst mixture downwardly to the central dehydrogenation/stripping stage.

Sapre, A.V.



Mechanistic interpretation of the effects of acid strength on alkane isomerization turnover rates and selectivity  

E-print Network

Keywords: Keggin polyoxometalates Heteropolyacids Skeletal isomerization Bifunctional catalysis Acid on bifunctional catalysts containing tungsten Keggin polyoxometalates (POM) with different central atoms func- tional theory (DFT) treatments for well-defined solid acids, such as Keggin polyoxometalate (POM

Iglesia, Enrique


Interaction of Peroxynitric Acid with Solid H2O Ice  

NASA Technical Reports Server (NTRS)

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.

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



Decolorization of Acid Red 1 by Fenton-like process using rice husk ash-based catalyst.  


The decolorization of Acid Red 1 (AR1) in aqueous solution was investigated by Fenton-like process. The effect of different reaction parameters such as different iron ions loading on rice husk ash (RHA), dosage of catalyst, initial pH, the initial hydrogen peroxide concentration ([H(2)O(2)](o)), the initial concentration of AR1 ([AR1](o)) and the reaction temperature on the decolorization of AR1 was studied. The optimal reacting conditions were found to be 0.070 wt.% of iron (III) oxide loading on RHA, dosage of catalyst=5.0 g L(-1), initial pH=2.0, [H(2)O(2)](o)=8 mM, [AR1](o)=50 mg L(-1) at temperature 30 degrees C. Under optimal condition, 96% decolorization efficiency of AR1 was achieved within 120 min of reaction. PMID:20042285

Daud, N K; Hameed, B H



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


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

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



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

SciTech Connect

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.

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



Formation of Linear Polyenes in Thermal Dehydration of Polyvinyl Alcohol, Catalyzed by Phosphotungstic Acid  

NASA Astrophysics Data System (ADS)

In order to obtain linear polyenes in polyvinyl alcohol films via acid-catalyzed thermal dehydration of the polyvinyl alcohol, we used phosphotungstic acid as the catalyst: a safe and heat-stable solid chemical compound. We established that phosphotungstic acid, introduced as solid nanoparticles into polyvinyl alcohol films, is a more effective dehydration catalyst than hydrochloric acid, since in contrast to HCl it does not evaporate from the film during heat treatment.

Tretinnikov, O. N.; Sushko, N. I.



Solar photocatalytic treatment of landfill leachate using a solid mineral by-product as a catalyst.  


The treatment of municipal solid waste landfill leachate in a pilot plant made up of solar compound parabolic collectors, using a solid industrial titanium by-product (WTiO(2)) containing TiO(2) and Fe(III) as a photocatalyst, was investigated. In the study evidence was found showing that the degradation performed with WTiO(2) was mainly due to the Fe provided by this by-product, instead of TiO(2). However, although TiO(2) had very little effect by itself, a synergistic effect was observed between Fe and TiO(2). The application of WTiO(2), which produced coupled photo-Fenton and heterogeneous catalysis reactions, achieved a surprisingly high depuration level (86% of COD removal), higher than that reached by photo-Fenton using commercial FeSO(4) (43%) in the same conditions. After the oxidation process the biodegradability and toxicity of the landfill leachate were studied. The results showed that the leachate biodegradability was substantially increased, at least in the first stages of the process, and again that WTiO(2) was more efficient than FeSO(4) in terms of increasing biodegradability. PMID:22633861

Poblete, Rodrigo; Prieto-Rodríguez, Lucia; Oller, Isabel; Maldonado, Manuel I; Malato, Sixto; Otal, Emilia; Vilches, Luis F; Fernández-Pereira, Constantino



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

NASA Astrophysics Data System (ADS)

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.

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



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

SciTech Connect

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.

Kim, H.; Kosuda, K. M.; Van Duyne, R. P.; Stair, P. C. (Chemical Sciences and Engineering Division); (Northwestern Univ.)



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)

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.

Jiang, Rongzhong; Chu, Deryn



Nano-Structured Solids and Heterogeneous Catalysts: Powerful Tools for the Reduction of CBRN Threats  

NASA Astrophysics Data System (ADS)

In the field of non-conventional CBRN weapons, the recent rapid development of nanotechnology and catalysis over nanosized solids provides innovative tools for the detection, protection and decontamination against these threats. By improving the efficiency of the countermeasures and by minimizing the negative effects of a deliberate use of CBRN agents, the practical application of the new technologies will readily represent a step forward in lowering the vulnerability of the civilian populations and in preventing the use of mass destruction weapons by terrorist groups or by `rogue states' supporting terrorists' activity. In such scenario, some relevant examples of nanosystems applied to the defense from non-conventional warfare agents will be here presented and commented. The key role of nanotechnology and heterogeneous catalysis for a multidisciplinary approach in counteracting CBRN threats will be highlighted too.

Guidotti, M.; Rossodivita, A.; Ranghieri, M. C.


Pd-modified Au on carbon as an effective and durable catalyst for the direct oxidation of HMF to 2,5-furandicarboxylic acid.  


Mixed noblility: We show that the modification of a gold/carbon catalyst with platinum or palladium produces stable and recyclable catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA): the support and nanoparticle chemistry directly mediate the selective oxidation of terminal hydroxyl groups in bio-derived HMF. This finding is a significant advance over current conversion technology because of the technological importance of FDCA. PMID:23495091

Villa, Alberto; Schiavoni, Marco; Campisi, Sebastiano; Veith, Gabriel M; Prati, Laura



Hazardous waste to materials: recovery of molybdenum and vanadium from acidic leach liquor of spent hydroprocessing catalyst using alamine 308.  


Recovery of valuable materials/metals from waste goes hand in hand with environmental protection. This paper deals with the development of a process for the recovery of metals such as Mo, V, Ni, Al from spent hydroprocessing catalyst which may otherwise cause a nuisance if dumped untreated. A detailed study on the separation of molybdenum and vanadium from the leach solution of spent hydroprocessing catalyst of composition: 27.15% MoO?, 1.7% V?O?, 3.75% NiO, 54.3% Al?O?, 2.3% SiO? and 10.4% LOI is reported in this paper. The catalyst was subjected to roasting under oxidizing atmosphere at a temperature of about 550 °C and leaching in dilute sulphuric acid to dissolve molybdenum, vanadium, nickel and part of aluminium. Metals from the leach solution were separated by solvent extraction. Both molybdenum and vanadium were selectively extracted with a suitable organic solvent leaving nickel and dissolved aluminium in the raffinate. Various parameters such as initial pH of the aqueous feed, organic to aqueous ratio (O:A), solvent concentration etc. were optimized for the complete extraction and recovery of Mo and V. Molybdenum and vanadium from the loaded organic were stripped by ammonia solution. They were recovered as their corresponding ammonium salt by selective precipitation, and were further calcined to get the corresponding oxides in pure form. PMID:23644591

Sahu, K K; Agrawal, Archana; Mishra, D



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

SciTech Connect

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).

Davis, Mark E.



Oxidation of ethane to ethylene and acetic acid by MoVNbO catalysts M. Roussel1  

E-print Network

ABSTRACT The influence of niobium on the physicochemical properties of the Mo-V-O system and on its that the most efficient formula was Mo0.73V0.18Nb0.9Oy. Acetic acid was formed at high pressure only. Analysis catalytic properties in the oxidation of ethane to ethylene and acetic acid is examined. Solids based on Mo

Paris-Sud XI, Université de


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

E-print Network

PHYSICAL STABILITY OF SPRAY 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...

Thybo, Pia



MOF-5 as an efficient heterogeneous catalyst for Friedel–Crafts alkylation reactions  

Microsoft Academic Search

A highly porous metal-organic framework (MOF-5) was synthesized by a solvothermal method, and used as an efficient heterogeneous acid catalyst for Friedel–Crafts alkylation reactions. The solid acid catalyst was characterized using a variety of different techniques, including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), atomic absorption spectrophotometry

Nam T. S. Phan; Ky K. A. Le; Tuan D. Phan



Phytase production and phytic acid reduction in rapeseed meal by Aspergillus niger during solid state fermentation  

Microsoft Academic Search

The effect of moisture content of media, glucose, phosphate, some surfactants and gamma irradiation on the production of phytase and reduction of phytic acid in rapeseed meal by Aspergillus niger A-98 (local isolate) during solid state fermentation have been considered. Optimum moisture content of media for these processes was 60%. Glucose concentrations of up to 6% in solid state culture

A. I El-Batal; H Abdel Karem



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


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

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



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

PubMed Central

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

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



Anaerobic Immobilized Yeast Cell Fermentation and Anaerobic Remediation in Hybrid Reactor for Mineralization of Dicarboxylic Acid Solid Waste  

Microsoft Academic Search

Summary  The solid resinous product (SRP) containing unsaturated\\/saturated dicarboxylic acid residues, phthalic acid and maleic acid\\u000a is discharged as a solid waste during cracking of benzene over vanadium at temperatures above 500°C in the dicarboxylic acid\\u000a manufacturing industry. In the present study the solid waste was diluted with water to a concentration of 0.5% w\\/v for microbial\\u000a degradation. The waste was

Ganesh Kumar Arumugam; Sekaran Ganesan; Swarnalatha Somasundaram; Prasad Rao Burusa



Waste shells of mollusk and egg as biodiesel production catalysts.  


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

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



Direct carbocyclizations of benzoic acids: catalyst-controlled synthesis of cyclic ketones and the development of tandem aHH (acyl Heck-Heck) reactions.  


The formation of exo-methylene indanones and indenones from simple ortho-allyl benzoic acid derivatives has been developed. Selective formation of the indanone or indenone products in these reactions is controlled by choice of ancillary ligand. This new process has a low environmental footprint as the products are formed in high yields using low catalyst loadings, while the only stoichiometric chemical waste generated from the reactants in the transformation is acetic acid. The conversion of the active cyclization catalyst into the Hermman-Beller palladacycle was exploited in a one-pot tandem acyl Heck-Heck (aHH) reaction, and utilized in the synthesis of donepezil. PMID:25047136

Miles, Kelsey C; Le, Chi Chip; Stambuli, James P



Polystyrene-bound Mn(T4PyP): a highly efficient and reusable catalyst for biomimetic oxidative decarboxylation of carboxylic acids with sodium periodate.  


In this report, highly efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by a supported manganese(III) porphyrin is described. In the presence of manganese(III) tetra(4-pyridyl)porphyrin supported on cross-linked chloromethylated polystyrene, [Mn(T4PyP)-CMP], as catalyst, carboxylic acids were converted to their corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate using imidazole as axial ligand. The oxidation of anti-inflammatory drugs such Indomethacin and Ibuprofen was carried out successfully and the decarboxylated products were obtained. This catalyst can be reused several times without loss of its catalytic activity in the oxidation reactions. PMID:19359183

Moghadam, Majid; Tangestaninejad, Shahram; Mirkhani, Valiollah; Mohammadpoor-Baltork, Iraj; Sirjanian, Narges; Parand, Somayeh



Biodiesel fuel production with solid superacid catalysis in fixed bed reactor under atmospheric pressure  

Microsoft Academic Search

Solid superacid catalysts of sulfated tin and zirconium oxides and tungstated zirconia are prepared and evaluated in the trans-esterification of soybean oil with methanol at 200–300 °C and the esterification of n-octanoic acid with methanol at 175–200 °C. Tungstated zirconia–alumina is a promising solid acid catalyst for the production of biodiesel fuels from soybean oil because of its high performance

Satoshi Furuta; Hiromi Matsuhashi; Kazushi Arata



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


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

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



Thermomorphic system with non-fluorous phase-tagged Ru(BINAP) catalyst: facile liquid/solid catalyst separation and application in asymmetric hydrogenation.  


The thermomorphic BINAP derivative 1 tagged with long alkyl chains was prepared from (S)-5,5'-diamino BINAP and applied to Ru-catalyzed asymmetric hydrogenation of beta-ketoesters under homogeneous conditions in 3:1 (v/v) ethanol/1,4-dioxane at 60 degrees C with high enantioselectivity (up to 98% ee). Results indicated that the Ru(1) catalyst was easily recovered by simple cooling and precipitation and could be used for at least four cycles without any loss of enantioselectivity. PMID:16555845

Huang, Yi-Yong; He, Yan-Mei; Zhou, Hai-Feng; Wu, Lei; Li, Bao-Lin; Fan, Qing-Hua



Pt-Ag catalysts as cathode material for oxygen-depolarized electrodes in hydrochloric acid electrolysis.  


Pt-Ag nanoparticles were prepared on a glassy carbon (GC) surface by pulsed electrodeposition and tested using cyclic voltammetry and scanning electrochemical microscopy (SECM) with respect to their possible use as catalyst material for oxygen reduction in 400 mM HCl solution. For comparison, a Pt catalyst was investigated under similar conditions. The redox competition mode of scanning electrochemical microscopy (RC-SECM) was adapted to the specific conditions caused by the presence of Cl(-) ions and used to visualize the local catalytic activity of the Pt-Ag deposits. Similarly prepared Pt deposits were shown to dissolve underneath the SECM tip. Pt-Ag composites showed improved long-term stability toward oxygen reduction as compared with Pt even under multiple switching off to open-circuit potential in 400 mM HCl. PMID:20146448

Maljusch, Artjom; Nagaiah, Tharamani Chikka; Schwamborn, Stefanie; Bron, Michael; Schuhmann, Wolfgang



Effects of potassium addition on the acidity and reducibility of chromia\\/alumina dehydrogenation catalysts  

Microsoft Academic Search

Dehydrogenation catalysts based on chromia supported on ?-alumina, containing about 6wt.% of chromium and increasing amounts of potassium (up to 1.8wt.%), were prepared and characterised by means of several techniques, such as N2 adsorption at 77K, X-ray powder diffraction (XRPD), UV-Vis diffuse reflectance spectroscopy (DRS), electron paramagnetic resonance (EPR), temperature programmed reduction (TPR), microcalorimetry and chemical analyses. The catalytic behaviour

E. Rombi; M. G. Cutrufello; V. Solinas; S. De Rossi; G. Ferraris; A. Pistone




Microsoft Academic Search

Mesoporous aluminosilicate catalysts having different Al\\/Si ratios were synthesized following a hydrothermal synthesis route and using different aluminum sources, such as aluminum nitrate and aluminum isopropoxide. These mesoporous materials have high surface areas, in the range of 520–1001 m\\/g, and exhibit Type IV nitrogen adsorption isotherms. EDS and Al MAS NMR results showed that aluminum was incorporated more effectively into the

Zeynep Obali; Naime Asli Sezgi; Timur Do?u



Clay Minerals as Solid Acids and Their Catalytic Properties.  

ERIC Educational Resources Information Center

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)

Helsen, J.



Citric acid production from carob pod by solid-state fermentation  

Microsoft Academic Search

The production of citric acid from carob pod by Aspergillus niger in solid-state fermentation was investigated. The maximal citric acid concentration (176 ± 4 g kg?1 dry pod), biomass dry weight (30 ± 0.7 g kg?1 wet substrate), citric acid yield (55 ± 2%), and sugar utilization (64 ± 2.5%) were obtained at a particle size of 0.5 mm, moisture

T. Roukas



Bio-inspired amino acid oxidation by a non-heme iron catalyst.  


This study reports the kinetics and mechanism of Fe(III)-catalyzed oxidative decarboxylation and deamination of a series of acyclic (?-aminoisobutyric acid, ?-(methylamino)isobutyric acid, alanine, norvaline, and 2-aminobutyric acid) and cyclic (1-aminocyclopropane-1-carboxylic acid, 1-amino-1-cyclobutanecarboxylic acid, 1-aminocyclopentanecarboxylic acid, and 1-aminocyclohexanecarboxylicacid) amino acids using hydrogen peroxide, t-butyl hydroperoxide, iodosylbenzene, m-chloroperbenzoic acid, and peroxomonosulphate as oxidant in 75% DMF-25% water solvent mixture. Model complex [Fe(IV)O(SALEN)](•+) (SALENH2: N,N'-bis(salicylidene)ethylenediamine) was generated by the reaction of Fe(III)(SALEN)Cl and H2O2 in CH3CN at 278 K as reported earlier. This method provided us high-valent oxoiron species, stable enough to ensure the direct observation of the reaction with amino acids. PMID:23528571

Góger, Szabina; Bogáth, Dóra; Baráth, Gábor; Simaan, A Jalila; Speier, Gábor; Kaizer, József



Influence of solid-state acidity on the decomposition of sucrose in amorphous systems. I.  


It was of interest to develop a method for solid-state acidity measurements using pH indicators and to correlate this method to the degradation rate of sucrose. Amorphous samples containing lactose 100mg/ml, sucrose 10mg/ml, citrate buffer (1-50mM) and sodium chloride (to adjust the ionic strength) were prepared by freeze-drying. The lyophiles were characterized using powder X-ray diffraction, differential scanning calorimetry and Karl Fischer titremetry. The solid-state acidity of all lyophiles was measured using diffuse reflectance spectroscopy and suitable indicators (thymol blue or bromophenol blue). The prepared lyophiles were subjected to a temperature of 60 degrees C and were analyzed for degradation using the Trinder kit. The results obtained from this study have shown that the solid-state acidity depends mainly on the molar ratio of the salt and the acid used in buffer preparation and not on the initial pH of the solution. The degradation of sucrose in the lyophiles is extremely sensitive to the solid-state acidity and the ionic strength. Reasonable correlation was obtained between the Hammett acidity function and sucrose degradation rate. The use of cosolvents (in the calibration plots) can provide good correlations with the rate of an acid-catalyzed reaction, sucrose inversion, in amorphous lyophiles. PMID:18647642

Alkhamis, Khouloud A



Preparation and characterization of mesoporous N-doped and sulfuric acid treated anatase TiO{sub 2} catalysts and their photocatalytic activity under UV and Vis illumination  

SciTech Connect

Nitrogen-doped TiO{sub 2} catalysts were prepared by a precipitation method. The samples were calcined at 400 deg. C for 4 h in air. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), low temperature N{sub 2}-adsorption was used for structural characterization and UV-diffuse reflectance (UV-DR) was applied to investigate the optical properties of the as-prepared samples. It was found that microporous N-doped catalysts have solely anatase crystalline structure. Acidic treatment of the calcined samples was performed using sulfuric acid agitation. The crystalline structure remained unchanged due to surface treatment, while the porosity and the surface areas (a{sub BET}{sup S}) were decreased dramatically. Optical characterization of the doped catalysts showed that they could be excited by visible light photons in the 400-500 nm wavelength range (lambda{sub g,1}={approx}390 nm, lambda{sub g,2}={approx}510 nm). It was also established that surface treatment enhances the Vis-light absorption of the N-TiO{sub 2} powders. Finally the catalysts were tested in the photocatalytic degradation of phenol in aqueous suspensions. Two different light sources were used; one of them was a UV-rich high pressure Hg-lamp, while the other was a tubular visible light source. We found that using visible light illumination N-doped, acid treated TiO{sub 2} samples were more catalytically active than non-doped TiO{sub 2} catalysts. - Graphical abstract: The effect of the acid treatment on the visible-light-driven photocatalytic activity of the N-doped, anatase TiO{sub 2} catalysts.

Kun, Robert [Supramolecular and Nanostructured Materials Research Group of the Hungarian Academy of Sciences, University of Szeged, Aradi vt. 1, H-6720 Szeged (Hungary); Tarjan, Sandor [Department of Colloid Chemistry, University of Szeged, Aradi vt. 1, H-6720 Szeged (Hungary); Oszko, Albert [Department of Solid State and Radiochemistry, University of Szeged, Aradi vt. 1, H-6720 Szeged (Hungary); Seemann, Torben; Zoellmer, Volker; Busse, Matthias [Fraunhofer Institute for Manufacturing Technology and Applied Materials Research, IFAM, Wienerstrasse 12, 28359 Bremen (Germany); Dekany, Imre, E-mail: i.dekany@chem.u-szeged.h [Supramolecular and Nanostructured Materials Research Group of the Hungarian Academy of Sciences, University of Szeged, Aradi vt. 1, H-6720 Szeged (Hungary); Department of Colloid Chemistry, University of Szeged, Aradi vt. 1, H-6720 Szeged (Hungary)



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)

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.

Robson, Michael H.


Vanadium Recovery by Leaching in Spent Catalysts for Sulfuric Acid Production Recuperação do Vanádio Contido em Catalisadores Gastos na Produção de Ácido Sulfúrico  

Microsoft Academic Search

Sulfuric acid plants often need catalyst replacement in order to cope with process improvements, removal of broken pellets, dust and moisture damaged particles. This removed material can not be discarded because has high amounts of vanadium. According to the Brazilian Environmental Authority this material must be stored under specified conditions. This situation requires large storing areas potentially useful for other



Influence of acid catalysts on the structural and magnetic properties of nanocrystalline barium ferrite prepared by sol–gel method  

Microsoft Academic Search

BaFe12O19 powders with nanocrystalline size were prepared by sol–gel techniques. Nitric, hydrochloric, acetic and stearic acid were used to improve the magnetic properties. Amorphous gels were formed with Fe\\/Ba molar ratio of 10.5. Then powders were obtained by subsequent heat treatment at 800–1000°C for 1h. Barium ferrite powder was also synthesized by solid state reaction at 1210°C. X-ray diffraction, scanning

Ebrahim Paimozd; Ali Ghasemi; Abdolhamid Jafari; Hassan Sheikh



Liquefaction with microencapsulated catalysts  


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.

Weller, Sol W. (Williamsville, NY)



Polystyrene-bound Mn(T4PyP): A highly efficient and reusable catalyst for biomimetic oxidative decarboxylation of carboxylic acids with sodium periodate  

Microsoft Academic Search

In this report, highly efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by a supported manganese(III) porphyrin is described. In the presence of manganese(III) tetra(4-pyridyl)porphyrin supported on cross-linked chloromethylated polystyrene, [Mn(T4PyP)-CMP], as catalyst, carboxylic acids were converted to their corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate using imidazole as axial ligand. The oxidation of anti-inflammatory drugs

Majid Moghadam; Shahram Tangestaninejad; Valiollah Mirkhani; Iraj Mohammadpoor-baltork; Narges Sirjanian; Somayeh Parand



Synthesis of tetrahydroisoquinolines and isochromans via Pictet–Spengler reactions catalyzed by Brønsted acid–surfactant-combined catalyst in aqueous media  

Microsoft Academic Search

Perfluorooctanesulfonic acid (PFOSA), Brønsted acid–surfactant-combined catalyst, efficiently catalyzes the Pictet–Spengler reactions of ?-arylethyl carbamate derivatives with aldehydes in water. The present reaction is accelerated by the addition of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). PFOSA in HFIP–water (10v\\/v%) is also successfully applied to the oxa-Pictet–Spengler reactions of ?-arylethyl alcohol compounds.

Akio Saito; Masaki Takayama; Aru Yamazaki; Junko Numaguchi; Yuji Hanzawa



Reduction of high content of free fatty acid in sludge palm oil via acid catalyst for biodiesel production  

Microsoft Academic Search

In this study, sulphuric acid (H2SO4) was used in the pretreatment of sludge palm oil for biodiesel production by an esterification process, followed by the basic catalyzed transesterification process. The purpose of the pretreatment process was to reduce the free fatty acids (FFA) content from high content FFA (>23%) of sludge palm oil (SPO) to a minimum level for biodiesel

Adeeb Hayyan; Mohamed E. S. Mirghani; Nassereldeen A. Kabbashi; Noor Irma Nazashida Mohd Hakimi; Yosri Mohd Siran; Shawaluddin Tahiruddin



6- endo-dig Cyclization of heteroarylesters to alkynes promoted by Lewis acid catalyst in the presence of Brønsted acid  

Microsoft Academic Search

We report a regiocontrolled 6-endo-dig cyclization of 2-(2-arylethynyl)heteroaryl esters occurred under Brønsted acidic conditions and in the presence of a catalytic amount of Lewis acids such as Cu(OTf)2, AuCl3, or (CF3CO2)Ag. A variety of heterocyclic lactones are readily prepared in excellent yields.

Malik Hellal; Jean-Jacques Bourguignon; Frédéric J.-J. Bihel



Solid-state 17O NMR of pharmaceutical compounds: salicylic acid and aspirin.  


We report solid-state NMR characterization of the (17)O quadrupole coupling (QC) and chemical shift (CS) tensors in five site-specifically (17)O-labeled samples of salicylic acid and o-acetylsalicylic acid (Aspirin). High-quality (17)O NMR spectra were obtained for these important pharmaceutical compounds under both static and magic angle spinning (MAS) conditions at two magnetic fields, 14.0 and 21.1 T. A total of 14 (17)O QC and CS tensors were experimentally determined for the seven oxygen sites in salicylic acid and Aspirin. Although both salicylic acid and Aspirin form hydrogen bonded cyclic dimers in the solid state, we found that the potential curves for the concerted double proton transfer in these two compounds are significantly different. In particular, while the double-well potential curve in Aspirin is nearly symmetrical, it is highly asymmetrical in salicylic acid. This difference results in quite different temperature dependencies in (17)O MAS spectra of the two compounds. A careful analysis of variable-temperature (17)O MAS NMR spectra of Aspirin allowed us to obtain the energy asymmetry (?E) of the double-well potential, ?E = 3.0 ± 0.5 kJ/mol. We were also able to determine a lower limit of ?E for salicylic acid, ?E > 10 kJ/mol. These asymmetrical features in potential energy curves were confirmed by plane-wave DFT computations, which yielded ?E = 3.7 and 17.8 kJ/mol for Aspirin and salicylic acid, respectively. To complement the solid-state (17)O NMR data, we also obtained solid-state (1)H and (13)C NMR spectra for salicylic acid and Aspirin. Using experimental NMR parameters obtained for all magnetic nuclei present in salicylic acid and Aspirin, we found that plane-wave DFT computations can produce highly accurate NMR parameters in well-defined crystalline organic compounds. PMID:23879687

Kong, Xianqi; Shan, Melissa; Terskikh, Victor; Hung, Ivan; Gan, Zhehong; Wu, Gang



Combination of CO{sub 2} reforming and partial oxidation of methane over NiO/MgO solid solution catalysts  

SciTech Connect

To overcome the explosions that can occur during the partial oxidation of methane, the latter exothermic reaction is coupled with an endothermic one, namely, the CO{sub 2} reforming of CH{sub 4}. These combined reactions have been carried out over NiO/MgO solid solution, NiO/Al{sub 2}O{sub 3}, and NiO/SiO{sub 2} catalysts. About 90% conversion of CH{sub 4} and about 98% selectivities to CO and H{sub 2} were obtained at 790 C and a GHSV (gas hourly space velocity) of 90,000 cm{sup 3}/g h (O{sub 2}/CO{sub 2}/CH{sub 4} = 14.5/26.9/58.6), over a reduced NiO/MgO solid solution catalyst. Almost no change in activity and selectivity occurred during 50 h of reaction. Compared to the reduced NiO/MgO, the reduced NiO/SiO{sub 2} and NiO/Al{sub 2}O{sub 3} catalysts provided lower activities and stabilities. The effects of the reaction temperature, space velocity, and feed gas composition for a ratio CH{sub 4}/(CO{sub 2} + 2O{sub 2}) = 1 were investigated. The increase in O{sub 2} in the feed gas resulted in a higher conversion of CH{sub 4}, but the apparent conversion of CO{sub 2} passed through a maximum. The CH{sub 4} conversion decreased with increasing space velocity, while during the partial oxidation, because of the hot spots, it would have increased. This means that the coupling can, indeed, control the thermal behavior of the reactor.

Ruckenstein, E.; Hu, Y.H. [State Univ. of New York, Amherst, NY (United States). Dept. of Chemical Engineering] [State Univ. of New York, Amherst, NY (United States). Dept. of Chemical Engineering



Depositional ice nucleation on solid ammonium sulfate and glutaric acid particles  

NASA Astrophysics Data System (ADS)

Heterogeneous ice nucleation on solid ammonium sulfate and solid amorphous 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 occurred preferentially on just a few ammonium sulfate and glutaric acid particles in each sample. For freezing temperatures between 214 K and 235 K average ice saturation ratios of S=1.10±0.07 for solid ammonium sulfate and S=1.39±0.16 for solid amorphous glutaric acid particles were determined. Experiments with externally mixed particles further show that ammonium sulfate is a more potent ice nucleus that 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 aerosol particles are available for ice formation. This pathway for ice formation may be particularly significant near the tropopause region where sulfates are abundant and other species known to be good ice nuclei are depleted.

Baustian, K. J.; Wise, M. E.; Tolbert, M. A.



Relationship between the number and strength of the acid sites on solid surfaces using ammonia adsorption  

SciTech Connect

A comparison of n-butylamine titrations with color indicators and gravimetric adsorption of ammonia on alumina, 12% molybdenum trioxide/alumina, 75Vertical Bar3< silica-alumina, and 12% molybdenum trioxide/75% silica-alumina gave the following relationship: pK/sub a/ = (11-1/x)/2 for ammonia adsorption at 200/sup 0/C, where x is the molar fraction of ammonia. The ammonia adsorption isotherm at 200/sup 0/C can thus be used for acid distribution determinations of colored catalysts.

Laine, J.; Yunes, S.; Brito, J.; Andreu, P.



Formation routes of interstellar glycine involving carboxylic acids: possible favoritism between gas and solid phase.  


Despite the extensive search for glycine (NH?CH?COOH) and other amino acids in molecular clouds associated with star-forming regions, only upper limits have been derived from radio observations. Nevertheless, two of glycine's precursors, formic acid and acetic acid, have been abundantly detected. Although both precursors may lead to glycine formation, the efficiency of reaction depends on their abundance and survival in the presence of a radiation field. These facts could promote some favoritism in the reaction pathways in the gas phase and solid phase (ice). Glycine and these two simplest carboxylic acids are found in many meteorites. Recently, glycine was also observed in cometary samples returned by the Stardust space probe. The goal of this work was to perform theoretical calculations for several interstellar reactions involving the simplest carboxylic acids as well as the carboxyl radical (COOH) in both gas and solid (ice) phase to understand which reactions could be the most favorable to produce glycine in interstellar regions fully illuminated by soft X-rays and UV, such as star-forming regions. The calculations were performed at four different levels for the gas phase (B3LYP/6-31G*, B3LYP/6-31++G**, MP2/6-31G*, and MP2/6-31++G**) and at MP2/6-31++G** level for the solid phase (ice). The current two-body reactions (thermochemical calculation) were combined with previous experimental data on the photodissociation of carboxylic acids to promote possible favoritism for glycine formation in the scenario involving formic and acetic acid in both gas and solid phase. Given that formic acid is destroyed more in the gas phase by soft X-rays than acetic acid is, we suggest that in the gas phase the most favorable reactions are acetic acid with NH or NH?OH. Another possible reaction involves NH?CH? and COOH, one of the most-produced radicals from the photodissociation of acetic acid. In the solid phase, we suggest that the reactions of formic acid with NH?CH or NH?CH?OH are the most favorable from the thermochemical point of view. PMID:22066498

Pilling, Sergio; Baptista, Leonardo; Boechat-Roberty, Heloisa M; Andrade, Diana P P



On the acidity of saponite materials: a combined HRTEM, FTIR, and solid-state NMR study.  


Acid clays were prepared by exchanging a synthetic saponite in HCl solutions of different concentration (0.01 and 1M, respectively). A combined experimental approach (XRD, HRTEM, N2 physisorption, solid-state MAS NMR, and TGA) was used to investigate on the structural, morphological, and textural features of the samples treated under mild and strong acid conditions. FTIR spectroscopy of adsorbed probe molecules with different basicity (e.g., CO and NH3) was used to monitor the surface acid properties and acid site distribution. XRD and SS-MAS NMR indicated that the activation under mild acid conditions does not alter the clay structure, while a deep modification of the saponite framework occurred after ion exchange in 1 M HCl solution. The presence of porous amorphous silica phase after treatment under strong acid conditions was confirmed by TEM inspection augmented by SS-MAS NMR and FTIR spectroscopy. N2 and Ar physisorption measurements suggested that cavitation phenomena occurred in saponite structure. N2 physisorption confirmed that the porosity and surface area of the samples are strongly modified upon strong acid treatment. FTIR spectroscopy of adsorbed NH3 pointed out that the H-exchange in mild conditions increased the number of surface Brønsted acid sites. Conversely, these sites are significantly depleted after treatment under strong acid conditions. The use of CO as a FTIR probe molecule, which is applied for the first time to study synthetic acid clays, allowed to monitor distribution and strength of Brønsted acid sites, whose acidity is similar to that of strong acid zeolites. The Al-OH sites with medium acidity are also found in acid-activated saponites. The distribution of strong and medium acid sites is strictly dependent on the acid conditions adopted. PMID:18251562

Bisio, C; Gatti, G; Boccaleri, E; Marchese, L; Bertinetti, L; Coluccia, S



Design and synthesis of palladium/graphitic carbon nitride/carbon black hybrids as high-performance catalysts for formic acid and methanol electrooxidation  

NASA Astrophysics Data System (ADS)

Here we report a facile two-step method to synthesize high-performance palladium/graphitic carbon nitride/carbon black (Pd/g-C3N4/carbon black) hybrids for electrooxidizing formic acid and methanol. The coating of g-C3N4 on carbon black surface is realized by a low-temperature heating treatment, followed by the uniform deposition of palladium nanoparticles (Pd NPs) via a wet chemistry route. Owning to the significant synergistic effects of the individual components, the preferred Pd/g-C3N4/carbon black electrocatalyst exhibits exceptional forward peak current densities as high as 2155 and 1720 mA mg-1Pd for formic acid oxidation in acid media and methanol oxidation in alkaline media, respectively, far outperforming the commercial Pd-C catalyst. The catalyst also shows reliable stability, demonstrating that the newly-designed hybrids have great promise in constructing high-performance portable fuel cell systems.

Qian, Huayu; Huang, Huajie; Wang, Xin



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.  


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

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



Domain-confined catalytic soot combustion over Co3O4 anchored on a TiO2 nanotube array catalyst prepared by mercaptoacetic acid induced surface-grafting.  


Herein, we introduce a specially designed domain-confined macroporous catalyst, namely, the Co3O4 nanocrystals anchored on a TiO2 nanotube array catalyst, which was synthesized by using the mercaptoacetic acid induced surface-grafting method. This catalyst exhibits much better performance for catalytic soot combustion than the conventional TiO2 powder supported one in gravitational contact mode (GMC). PMID:24177172

Ren, Jiale; Yu, Yifu; Dai, Fangfang; Meng, Ming; Zhang, Jing; Zheng, Lirong; Hu, Tiandou



Enhanced production of ganoderic acids and cytotoxicity of Ganoderma lucidum using solid-medium culture.  


Submerged cultures of Ganoderma lucidum are used to produce fungal mycelium, which is used as a functional food and in the production of various triterpenoids, including ganoderic acids (GAs). Specific culture approaches that produce fungal mycelium with high levels of GAs and good biological activity are critical in the functional food industry. In this study, a solid-medium culture approach to producing mycelium was compared to the submerged culture system. Production of GAs, biomass, intracellular polysaccharides, and cytotoxicity of the cultured mycelium were compared as between solid and submerged culture. Growing G. lucidum strains on solid potato dextrose agar medium increased biomass, the production of ganoderic acid 24 (lanosta-7,9(11), 24-trien-3?-o1-26-oic acid), GAs, and total intracellular polysaccharides as compared to fungi grown in submerged culture. Triterpenoid-enriched methanol extracts of mycelium from solid-medium culture showed higher cytotoxicity than those from submerged culture. The IC(50) values of methanol extracts from solid-medium culture were 11.5, 8.6, and 9.9 times less than submerged culture on human lung cancer cells CH27, melanoma cells M21, and oral cancer cells HSC-3 respectively. The squalene synthase and lanosterol synthase coding genes had higher expression on the culture of solid potato dextrose medium. This is the first report that solid-medium culture is able to increase GA production significantly as compared to submerged culture and, in the process, produces much higher biological activity. This indicates that it may be possible to enhance the production of GAs by implementing mycelium culture on solid medium. PMID:22878212

You, Bang-Jau; Lee, Hong-Zin; Chung, Kuang-Ren; Lee, Miin-Huey; Huang, Mei-Jung; Tien, Ni; Chan, Chiao-Wei; Kuo, Yueh-Hsiung



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.  


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

Corradini, Patricia Gon; Antolini, Ermete; Perez, Joelma



Monomeric metal aqua complexes in the interlayer space of montmorillonites as strong Lewis acid catalysts for heterogeneous carbon-carbon bond-forming reactions.  


Montmorillonite-enwrapped copper and scandium catalysts (Cu(2+)- and Sc(3+)-monts) were easily prepared by treating Na(+)-mont with the aqueous solution of the copper nitrate and scandium triflate, respectively. The resulting Cu(2+)- and Sc(3+)-monts showed outstanding catalytic activities for a variety of carbon-carbon bond-forming reactions, such as the Michael reaction, the Sakurai-Hosomi allylation, and the Diels-Alder reaction, under solvent-free or aqueous conditions. The remarkable activity of the mont catalysts is attributable to the negatively charged silicate layers that are capable of stabilizing metal cations. Furthermore, these catalysts were reusable without any appreciable loss in activity and selectivity. The Cu(2+)-mont-catalyzed Michael reaction proceeds via a ternary complex in which both the 1,3-dicarbonyl compound and the enone are coordinated to a Lewis acid Cu(2+) center. PMID:15551316

Kawabata, Tomonori; Kato, Masaki; Mizugaki, Tomoo; Ebitani, Kohki; Kaneda, Kiyotomi



An NMR study of acid sites on chlorided alumina catalysts using trimethylphosphine as a probe  

Microsoft Academic Search

The MAS-NMR spectra of adsorbed trimethylphosphine (TMP) were used to determine the concentration of Brønsted and Lewis acid sites on pure and chlorinated?-Al2O3 samples. Chlorination with CHCl3,CCl4 or AlCl3 promoted the formation of Brønsted acid centers, which are characterized by the protonated adduct of TMP. This adduct has a31P chemical shift of ca. -3.8 ppm and a JP-H scalar coupling

Hong Sang; Hon Yue Chu; Jack H. Lunsford



3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid.  


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

Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit; Baranova, Elena A; Santinacci, Lionel



Economic impact of total solids loading on enzymatic hydrolysis of dilute acid pretreated corn stover.  


In process integration studies of the biomass-to-ethanol conversion process, it is necessary to understand how cellulose conversion yields vary as a function of solids and enzyme loading and other key operating variables. The impact of solids loading on enzymatic cellulose hydrolysis of dilute acid pretreated corn stover slurry was determined using an experimental response surface design methodology. From the experimental work, an empirical correlation was obtained that expresses monomeric glucose yield from enzymatic cellulose hydrolysis as a function of solids loading, enzyme loading, and temperature. This correlation was used in a technoeconomic model to study the impact of solids loading on ethanol production economics. The empirical correlation was used to provide a more realistic assessment of process cost by accounting for changes in cellulose conversion yields at different solids and enzyme loadings as well as enzyme cost. As long as enzymatic cellulose conversion drops off at higher total solids loading (due to end-product inhibition or other factors), there is an optimum value for the total solids loading that minimizes the ethanol production cost. The optimum total solids loading shifts to higher values as enzyme cost decreases. PMID:20945482

Humbird, David; Mohagheghi, Ali; Dowe, Nancy; Schell, Daniel J



Altered chemical and biological activities of all- trans retinoic acid incorporated in solid lipid nanoparticle powders  

Microsoft Academic Search

The principal aim of this study was to investigate whether the solid lipid nanoparticle (SLN) powder formulation of all-trans retinoic acid (ATRA) can favorably alter the chemical stability and biological activities of ATRA. SLN powder formulation of ATRA was obtained by freeze-drying of SLN dispersions. The chemical stability of ATRA was determined by HPLC analysis. The anticancer efficacy of ATRA

Soo-Jeong Lim; Mi-Kyung Lee; Chong-Kook Kim



Aqueous and solid complexes of iron(III) with hyaluronic acid  

Microsoft Academic Search

The coordination of iron(III) ion to hyaluronic acid (Hyal) in aqueous solutions and solid state was accomplished by potentiometric titrations and infrared spectroscopy. The potentiometric titration studies provided the binding constants for the complexes found in the systems and the speciation of these species according to the variation of pH values. The complexes found presented a complexing ability through both

Ana Lucia Ramalho Mercê; Luiz Carlos Marques Carrera; Lilian Kelly Santos Romanholi; Mar??a Ángeles Lobo Recio



Halogen bond induced phosphorescence of capped ?-amino acid in the solid state.  


The Boc and N,N'-dicyclohexylurea capped ?-amino acid upon monobromination showed phosphorescence in the solid state. The compound exhibited different photoluminescence intensity and lifetimes in crystals obtained from ethyl acetate and methanol. X-ray crystallography revealed that the intermolecular C=O…Br halogen bond directs the heavy atom effect to produce the phosphorescence. PMID:23985996

Maity, Suman Kumar; Bera, Santu; Paikar, Arpita; Pramanik, Apurba; Haldar, Debasish



Matrix solid-phase dispersion for the liquid chromatographic determination of phenolic acids in Melissa officinalis  

Microsoft Academic Search

Matrix solid-phase dispersion (MSPD) was used for sample preparation of plant material (Melissa officinalis, Lemon Balm) prior to liquid chromatography of rosmarinic, caffeic and protocatechuic acids, phenolic compounds present in this herb. Different MSPD sorbents and various elution agents were tested and the optimal extraction conditions determined with the aim to obtain extraction recoveries greater than 90% for all analytes.

Alica Žiaková; Eva Brandšteterová; Eva Blahová



Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes  

E-print Network

Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes Sossina Ma The compound CsH2PO4 has emerged as a viable electrolyte for intermediate temperature (200­300 1C cells, in which a composite mixture of the electrolyte, Pt supported on carbon, Pt black and carbon


Vibrational spectroscopic study on polymorphism of erucic acid and palmitoleic acid: ?1??1 and ??? reversible solid state phase transitions  

NASA Astrophysics Data System (ADS)

The infrared and Raman spectra of four polymorphic phases (?, ?1, ? and ?1) of erucic acid ( cis-13-docosenoic acid) and those of two polymorphic phases (? and ?) of palmitoleic acid ( cis-9-hexadecenoic acid) were investigated. The ? and ?1 phases of erucic acid were analyzed on the basis of crystal structures determined by us. There were large spectral differences between ? and ?1 phases, which could be ascribed to the differences in the conformation of cis-olefin groups and the subcell structure. Two types of reversible solid state phase transitions (??? and ?1??1 transitions) were followed by the infrared and Raman spectra. It was concluded that the mechanism of the ??? phase transition of erucic and palmitoleic acids is essentially the same as that of oleic acid previously reported by us [ J. Phys. Chem.90, 6371 (1986)], i.e. this phase transition is of order-disorder type accompanied by a conformational disordering at the methyl-terminal chain. Spectral changes on the ?1??1 transition suggested that a similar structural change took place during this transition but there were large structural differences between ? and ?1.

Kaneko, Fumitoshi; Yamazaki, Kazuhiro; Kobayashi, Masamichi; Sato, Kiyotaka; Suzuki, Masao



Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane  

SciTech Connect

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.

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



Oxidative Degradation of Different Chlorinated Phenoxyalkanoic Acid Herbicides by a Hybrid ZrO2 Gel-Derived Catalyst without Light Irradiation.  


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

Sannino, Filomena; Pernice, Pasquale; Minieri, Luciana; Camandona, Gaia Aurora; Aronne, Antonio; Pirozzi, Domenico



Effects of natural water ions and humic acid on catalytic nitrate reduction kinetics using an alumina supported Pd-Cu catalyst.  


Catalytic nitrate reduction was evaluated for the purpose of drinking water treatment. Common anions present in natural waters and humic acid were evaluated for their effects on NO3(-) hydrogenation over a bimetallic supported catalyst (Pd-Cu/gamma-Al2O3). Groundwater samples, with and without powder activated carbon (PAC) pretreatment, were also evaluated. In the absence of inhibitors the NO3- reduction rate was 2.4 x 10(-01) L/min g cat. However, the addition of constituents (SO4(2-), SO3(2-), HS-, CI-, HCO3-, OH-, and humic acid) on the order of representative concentrations for drinking water decreased the NO3- reduction rate. Sulfite, sulfide, and elevated chloride decreased the NO3- reduction rate by over 2 orders of magnitude. Preferential adsorption of Cl- inhibited NO3- reduction to a greater extent than NO2- reduction. Partial regeneration of catalysts exposed to SO3(2-) was achieved by using a dilute hypochlorite solution, however Cu dissolution occurred. Dissolved constituents in the groundwater sample decreased the NO3- reduction rate to 3.7 x 10(-03) L/min g cat and increased ammonia production. Removal of dissolved organic matter from the groundwater using PAC increased the NO3- reduction rate to 5.06 x 10(-02) L/min g cat and decreased ammonia production. Elemental analyses of catalysts exposed to the natural groundwater suggest that mineral precipitation may also contribute to catalyst fouling. PMID:16719114

Chaplin, Brian P; Roundy, Eric; Guy, Kathryn A; Shapley, John R; Werth, Charles J



Catalyst Alloys Processing  

NASA Astrophysics Data System (ADS)

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.

Tan, Xincai



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

SciTech Connect

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.

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



One-Pot Synthesis of ?-Acetamido Ketones Using Boric Acid at Room Temperature  

PubMed Central

?-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

Karimi-Jaberi, Zahed; Mohammadi, Korosh



Oxidation catalyst  


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.

Ceyer, Sylvia T. (Cambridge, MA); Lahr, David L. (Cambridge, MA)



Effects of polyurethane matrices on fungal tannase and gallic acid production under solid state culture.  


The influence of the physical structure of polyurethane matrix as a support in a solid state culture in tannase production and gallic acid accumulation by Aspergillus niger Aa-20 was evaluated. Three different polyurethane matrices were used as the support: continuous, semi-discontinuous and discontinuous. The highest tannase production at 2479.59 U/L during the first 12 h of culture was obtained using the discontinuous matrix. The gallic acid was accumulated at 7.64 g/L at the discontinuous matrix. The results show that the discontinuous matrix of polyurethane is better for tannase production and gallic acid accumulation in a solid state culture bioprocess than the continuous and semi-discontinuous matrices. PMID:17910122

Trevino, Lucia; Contreras-Esquivel, Juan C; Rodríguez-Herrera, Raul; Aguilar, Cristóbal Noé



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


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

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



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...


Determination of vitamin K 1 in emulsified nutritional supplements by solid-phase extraction and high-performance liquid chromatography with postcolumn reduction on a platinum catalyst and fluorescece detection  

Microsoft Academic Search

Determination of small amounts of vitamin K1 (0.8 ?g\\/g) in nutritional supplements with high fat content (20 mg\\/g) was performed by solid-phase extraction and high-performance liquid chromatography (HPLC) with fluorescence detection after reduction on a platinum oxide catalyst. The concentration ratio of plant oils to vitamin K1 (0.8 ?g\\/g) was about 25?000:1. A sample solution was applied to a solid-phase

Hiroshi Iwase



Combination of best promoter and micellar catalyst for more than kilo-fold rate acceleration in favor of chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media at room temperature  

NASA Astrophysics Data System (ADS)

Picolinic acid, 2,2?-bipyridine and 1,10-phenanthroline promoted Cr(VI) oxidation of D-galactose to D-galactonic acid in three representative aqueous micellar media has been studied. The anionic surfactant (SDS) accelerated the rate of reaction while the cationic surfactant (CPC) and neutral surfactant (TX-100) retarded the reaction rate. Combination of bipy and SDS is the best choice for chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media although 1,10-phenanthroline is best promoter in absence of micellar catalyst.

Saha, Rumpa; Ghosh, Aniruddha; Sar, Pintu; Saha, Indrajit; Ghosh, Sumanta K.; Mukherjee, Kakali; Saha, Bidyut



Combination of best promoter and micellar catalyst for more than kilo-fold rate acceleration in favor of chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media at room temperature.  


Picolinic acid, 2,2'-bipyridine and 1,10-phenanthroline promoted Cr(VI) oxidation of D-galactose to D-galactonic acid in three representative aqueous micellar media has been studied. The anionic surfactant (SDS) accelerated the rate of reaction while the cationic surfactant (CPC) and neutral surfactant (TX-100) retarded the reaction rate. Combination of bipy and SDS is the best choice for chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media although 1,10-phenanthroline is best promoter in absence of micellar catalyst. PMID:23978739

Saha, Rumpa; Ghosh, Aniruddha; Sar, Pintu; Saha, Indrajit; Ghosh, Sumanta K; Mukherjee, Kakali; Saha, Bidyut



Effects of metal ions on the hydrolysis of bamboo biomass in 1-butyl-3-methylimidazolium chloride with dilute acid as catalyst.  


In this study, the effects of six metal ions including Na+, K+, Mg2+, Ca2+, Cu2+ and Fe3+ on hydrolysis of bamboo biomass by diluted hydrochloride acid (HCl) in ionic liquid [C4mim]Cl under mild conditions was investigated. These metal ions as co-catalysts exhibited significant effects on accelerating the hydrolysis process and improving the yield of total reducing sugar compared to single diluted hydrochloride acid hydrolysis in [C4mim]Cl at the same conditions. The most effective ion was Cu2+ and the total reducing sugar yield of 67.1% was achieved at 100 °C with CuCl2 as co-catalyst after 4-h reaction. The total reducing sugar yield was increased by about 7% and the reaction time was decreased by 3 h. The kinetic model was also investigated to give an insight into the mechanism of hydrolysis process. PMID:25444883

Wang, Nan; Zhang, Jie; Wang, Honghui; Li, Qiang; Wei, Sun'an; Wang, Dan



Sonochemical synthesis of silica and silica sulfuric acid nanoparticles from rice husk ash: a new and recyclable catalyst for the acetylation of alcohols and phenols under heterogeneous conditions.  


Silica nanoparticles were synthesized from rice husk ash at room temperature by sonochemical method. The feeding rate of percipiteting agent and time of sonication were investigated. The nanostructure of the synthesized powder was realized by the FE-SEM photomicrograph, FT-IR spectroscopy, XRD and XRF analyses. These analytical observations have revealed that the nano-sized amorphous silica particles are formed and they are spheroidal in shape. The average particle size of the silica powders is found to be around 50 nm. The as-synthesized silica nanoparticles were subsequently modified with chlorosulfonic acid and prepared silica sulfuric acid nanoparticles, which were employed as an efficient catalyst for the acylation of alcohols and phenols with acetic anhydride in excellent yields under solvent-free conditions at room temperature. This reported method is simple, mild, and environmentally viable and catalyst can be simply recovered and reused over 9 times without any significant loss of its catalytic activity. PMID:22934954

Salavati-Niasari, Masoud; Javidi, Jaber



Furfural modified asphalt obtained by using a Lewis acid as a catalyst  

SciTech Connect

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.

Memon, G.M. [FHWA/EBA Engineering Inc., McLean, VA (United States); Chollar, B.H. [FHWA, McLean, VA (United States)



Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition  

PubMed Central

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids. PMID:25080007

Nakayama, Hirokazu; Hayashi, Aki



Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells  

NASA Technical Reports Server (NTRS)

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.

Stonehart, P.; Baris, J.; Hockmuth, J.; Pagliaro, P.



Catalyst-free tandem Michael addition/decarboxylation of (thio)coumarin-3-carboxylic acids with indoles: facile synthesis of indole-3-substituted 3,4-dihydro(thio)coumarins.  


The tandem Michael addition/decarboxylation of (thio)coumarin-3-carboxylic acids with indoles has been developed and the biologically important indole-3-substituted dihydrocoumarins were obtained in good to excellent yields under catalyst-free conditions. PMID:24589942

Shao, Zhuzhou; Xu, Lubin; Wang, Liang; Wei, Hongtao; Xiao, Jian



Radionuclide Leaching from Residual Solids Remaining after Acid Dissolution of Composite K East Canister Sludge  

SciTech Connect

Laboratory tests were performed to examine mixed nitric/hydrofluoric acid leach treatments for decontaminating dissolver residual solids (KECDVSR24H-2) produced during a 20- to 24-hr dissolution of a composite K East (KE) Basin canister sludge in 95 C 6 M nitric acid (HNO{sub 3}). The scope of this testing has been described in Section 4.5 of ''Testing Strategy to Support the Development of K Basin Sludge Treatment Process'' (Flament 1998). Radionuclides sorbed or associated with the residual solids generated in the K Basin sludge treatment process can restrict disposal of this solid to the Environmental Restoration Disposal Facility (ERDF). The starting dissolver residual solid for this testing, KECDVSR24H-2, contains radionuclides at concentrations which exceed the ERDF Waste Acceptance Criteria for TRU by about a factor of 70, for {sup 239}Pu by a factor of 200, and for {sup 241}Am by a factor of 50. The solids also exceed the ERDF criterion for {sup 137}Cs by a factor of 2 and uranium by a factor of 5. Therefore, the radionuclides of greatest interest in this leaching study are first {sup 239}Pu and {sup 241}Am (both components of TRU) and then uranium and {sup 137}Cs.

Delegard, C.H.; Rinehart, D.E.; Soderquist, C.Z.; Fadeff, S.K.



Lewis acid catalyzed reactions of chiral imidazolidinones and oxazolidinones: insights on the role of the catalyst.  


The mechanism proposed by Evans to justify the selectivity obtained in Lewis acid catalyzed Diels-Alder reactions of cyclopentadiene with acyloxazolidinones has been generalized and used in the rationalization of selectivities obtained in many other systems. However, we recently proposed an alternative mechanism, on the basis of open-chain mono- and bicomplexes, that avoids the need for chelates and explains the selectivity obtained by Evans. In this manuscript we apply our proposal to the catalyzed conjugated addition of amines to acylimidazolidinones, reported by Cardillo, and we clearly show that aluminum chelates are not involved in the reaction, as they induce no selectivity, while Cardillo observed high experimental selectivities. Our data equally show that bicomplexes with carbonyl parallel orientation, proposed by Cardillo to justify the experimental selectivity with nonchelating Lewis acids, indeed induce the opposite selectivity and have also to be dismissed. On the other hand, our mechanistic proposal allows for the full rationalization of the data obtained by Cardillo with aluminum, boron, or zinc Lewis acids and supports our previous proposal on DA cycloadditions of dienes to Evans chiral auxiliary derivatives. PMID:21786834

Duarte, Filipe J S; Bakalova, Snezhana M; Cabrita, Eurico J; Santos, A Gil



Development of a Ni-Ce0.8Zr0.2O2 catalyst for solid oxide fuel cells operating on ethanol through internal reforming  

NASA Astrophysics Data System (ADS)

Inexpensive 20 wt.% Ni-Ce0.8Zr0.2O2 catalysts are synthesized by a glycine nitrate process (GNP) and an impregnation process (IMP). The catalytic activity for ethanol steam reforming (ESR) at 400-650 °C, catalytic stability and carbon deposition properties are investigated. Ni-Ce0.8Zr0.2O2 (GNP) shows a higher catalytic performance than Ni-Ce0.8Zr0.2O2 (IMP), especially at lower temperatures. It also presents a better coking resistance and a lower graphitization degree of the deposited carbon. The superior catalytic activity and coke resistance of Ni-Ce0.8Zr0.2O2 (GNP) is attributed to the small particle size of the active metallic nickel phase and the strong interaction between the nickel and the Ce0.8Zr0.2O2 support, as evidenced by the XRD and H2-TPR. The Ni-Ce0.8Zr0.2O2 (GNP) is further applied as an anode functional layer in solid oxide fuel cells operating on ethanol steam. The cell yields a peak power density of 536 mW cm-2 at 700 °C when operating on EtOH-H2O gas mixtures, which is only slightly lower than that of hydrogen fuel, whereas the cell without the functional layer failed for short-term operations. Ni-Ce0.8Zr0.2O2 (GNP) is promising as an active and highly coking-resistant catalyst layer for solid-oxide fuel cells operating on ethanol steam fuel.

Liao, Mingming; Wang, Wei; Ran, Ran; Shao, Zongping



One-pot synthesis of dihydropyrimidones using silica-supported heteropoly acid as an efficient and reusable catalyst: Improved protocol conditions for the Biginelli reaction  

Microsoft Academic Search

An efficient synthesis of 3,4-dihydropyrimidinones or thiones (DHPMs) is described, using silica-supported heteropoly acid H3PW12O40\\/SiO2 (PW\\/SiO2) for the first time as the catalyst from an aldehyde, ?-keto ester and urea or thiourea in acetonitrile. Compared to the classical Biginelli reaction conditions, this method consistently has the advantage of excellent yields, mild reaction conditions, ease of workup, survival of different functional

Ezzat Rafiee; Fomaida Shahbazi



Perfluorosulfonic acid membrane catalysts for optical sensing of anhydrides in the gas phase.  


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

Ayyadurai, Subasri M; Worrall, Adam D; Bernstein, Jonathan A; Angelopoulos, Anastasios P



Depositional ice nucleation on solid ammonium sulfate and glutaric acid particles  

NASA Astrophysics Data System (ADS)

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.

Baustian, K. J.; Wise, M. E.; Tolbert, M. A.



Preparation and characterization of hydrophobic TiO(2) pillared clay: the effect of acid hydrolysis catalyst and doped Pt amount on photocatalytic activity.  


Titanium hydrate sols were prepared using different acid hydrolysis catalysts, i.e., acetic acid and hydrochloric acid. The platinum-doped TiO(2) sol-gels were also synthesized by adding K(2)PtCl(6) into the titanium hydrate sols. The hydrophobic montmorillonite clay, treated with organic cationic surfactant, i.e., hexadecyltrimethylammonium bromide, was used as a template to prepare TiO(2) pillared photocatalyst with the above sols. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX) were employed to characterize the resulting photocatalysts. The adsorption performance and photoactivity of prepared pillared clays were studied by using methyl orange as a model organic pollutant. The preliminary results indicated that the hydrophobic TiO(2) pillared clay prepared with acetic acid as the acid hydrolysis catalysts possessed higher photocatalytic activity than that with hydrochloric acid. Due to the excellent sedimentation property of the clay, the resulting pillared photocatalyst is easily recovered and reused in the postrun treatment. Also the doping of platinum into the hydrophobic photocatalyst can increase the photocatalytic activity significantly. PMID:18279880

Ding, Xuejun; An, Taicheng; Li, Guiying; Zhang, Shanqing; Chen, Jiaxin; Yuan, Jianmei; Zhao, Huijun; Chen, Hui; Sheng, Guoying; Fu, Jiamo



2H-solid state NMR and DSC study of isobutyric acid in mesoporous silica materials.  


Solid state deuterium NMR has been used to study the molecular motion of d(6)-isobutyric acid (d(6)-iBA) in the pure (unconfined) state and confined in the cylindrical pores of two periodic mesoporous silica materials (MCM-41, pore size 3.3 nm and SBA-15, pore size 8 nm), and in a controlled pore glass (CPG-10-75, pore size ca. 10 nm). The line shape analysis of the spectra at different temperatures revealed three rotational states of the iBA molecules: liquid (fast anisotropic reorientation of the molecule), solid I (rotation of the methyl group) and solid II (no rotational motion on the time scale of the experiment). Transition temperatures between these states were determined from the temperature dependence of the fraction of molecules in these states. Whereas the solid I-solid II transition temperature is not affected by confinement, a significant lowering of the liquid-solid I transition temperature in the pores relative to the bulk acid was found for the three matrix materials, exhibiting an unusual dependence on pore size and pore morphology. Complementary DSC measurements on the same systems show that the rotational melting (solid I-liquid) of d(6)-iBA in the pores occurs at a temperature 20-45 K below the thermodynamic melting point. This finding indicated that the decoupling of rotational and translational degrees of freedom in phase transitions in confined systems previously found for benzene is not restricted to molecules with non-specific interactions, but represents a more general phenomenon. PMID:17487322

Vyalikh, A; Emmler, Th; Shenderovich, I; Zeng, Y; Findenegg, G H; Buntkowsky, G



Chiral salen-metal complexes as novel catalysts for asymmetric phase transfer alkylations  

Microsoft Academic Search

Chiral, salen-metal complexes have been tested as catalysts for the C-alkylation of aldimine Schiff's bases of alanine esters with alkyl bromides under phase-transfer conditions (solid sodium hydroxide, toluene, ambient temperature, 1–10% of the catalyst). The best catalyst, which was derived from a Cu(II) complex of (1R,2R or 1S,2S)-[N,N?-bis(2?-hydroxybenzylidene)]-1,2-diaminocyclohexane, gave ?-methyl-?-amino acids with enantiomeric excesses of 70–96%.

Yuri N. Belokon; Michael North; Vadim S. Kublitski; Nikolai S. Ikonnikov; Pavel E. Krasik; Viktor I. Maleev



Metal-loaded CeO 2-ZrO 2 solid solutions as innovative catalysts for automotive catalytic converters  

Microsoft Academic Search

The redox behaviour of a Ce0.5Zr0.5O2 solid solution is investigated by means of temperature programmed reduction (TPR) and oxygen uptake measurements. It is shown that the introduction of ZrO2 into the CeO2 framework, strongly modifies the reduction behaviour in comparison to pure CeO2. Remarkably, in contrast to the CeO2, upon repetitive reduction-oxidation processes, the temperature of reduction of the solid

Paolo Fornasiero; Gabriele Balducci; Sergio Meriani; Roberta di Monte; Mauro Graziani



Iron oxide nanoparticles immobilized to mesoporous NH2-SiO2 spheres by sulfonic acid functionalization as highly efficient catalysts  

NASA Astrophysics Data System (ADS)

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

Zhang, Guoliang; Qin, Lei; Wu, Yujiao; Xu, Zehai; Guo, Xinwen



A Phase I Protocol of Hydralazine and Valproic Acid in Advanced, Previously Treated Solid Cancers.  


Smokers experience aberrant gene promoter methylation in their bronchial cells, which may predispose to the development of neoplasia. Hydralazine is a DNA demethylating agent, and valproic acid is a histone deacetylase inhibitor, and both have modest but synergistic anticancer activity in vitro. We conducted a phase I trial combining valproic acid and hydralazine to determine the maximally tolerated dose (MTD) of hydralazine in combination with a therapeutic dose of valproic acid in patients with advanced, unresectable, and previously treated solid cancers. Twenty females and nine males were enrolled, with a median age of 57 years and a median ECOG performance status of 0. Grade 1 lymphopenia and fatigue were the most common adverse effects. Three subjects withdrew for treatment-related toxicities occurring after the DLT observation period, including testicular edema, rash, and an increase in serum lipase accompanied by hyponatremia in one subject each. A true MTD of hydralazine in combination with therapeutic doses of valproic acid was not reached in this trial, and the planned upper limit of hydralazine investigated in this combination was 400 mg/day without grade 3 or 4 toxicities. A median number of two treatment cycles were delivered. One partial response by Response Evaluation Criteria In Solid Tumors criteria was observed, and five subjects experienced stable disease for 3 to 6 months. The combination of hydralazine and valproic acid is simple, nontoxic, and might be appropriate for chemoprevention or combination with other cancer treatments. This trial supports further investigation of epigenetic modification as a new therapeutic strategy. PMID:24746712

Bauman, Julie; Shaheen, Monte; Verschraegen, Claire F; Belinsky, Steven A; Houman Fekrazad, M; Lee, Fa-Chyi; Rabinowitz, Ian; Ravindranathan, Meera; Jones, Dennie V



The solid-state structure of calix[4]arene dihydroxyphosphonic acid- L-lysine complex  

NASA Astrophysics Data System (ADS)

The solid-state structure of calix[4]arene dihydroxyphosphonic acid with L-lysine shows a high degree of complexity. The system presents three independent molecules of amino acid, all in different conformational structures, associated with four molecules of calixarene, in the presence of a relatively high number of solvent molecules. The general topology of the complex is guided by the layer of two dimeric units of calixarene molecules and by the large network of hydrogen bonds generated by the molecules of lysine. The arrangement of lysine molecules in the crystal generates a 1-D ladder network.

Lazar, Adina N.; Danylyuk, Oksana; Suwinska, Kinga; Coleman, Anthony W.



Conversion of municipal solid waste into carboxylic acids by anaerobic countercurrent fermentation  

Microsoft Academic Search

Municipal solid waste (MSW) and sewage sludge (SS) were combined and anaerobically converted into carboxylate salts by using\\u000a a mixed culture of acid-forming microorganisms. MSW is an energy source and SS is a source of nutrients. In this study, MSW\\u000a and SS were combined, so they complemented each other. Four fermentors were arranged in series for a countercurrent fermentation\\u000a process.

Cateryna Aiello-Mazzarri; Guillermo Coward-Kelly; Frank K. Agbogbo; Mark T. Holtzapple



Polyunsaturated fatty acids production with a solid-state column reactor  

Microsoft Academic Search

To investigate the potential production of polyunsaturated fatty acids (PUFAs), a solid-state column reactor of rice bran with Mortierella alpina was used. The optimal conditions for PUFAs production were rice bran supplementation with 3.75% (ww?1) nitrogen source at initial moisture content 57%, initial pH 6–7, aeration, and incubation at 20°C for 5 days and then at 12°C for 7 days.

Hung-Der Jang; Shang-Shyng Yang



Prototype demonstration of dual sorbent injection for acid gas control on municipal solid waste combustion units  

SciTech Connect

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.




Solid-state NMR analyses reveal the structure dependence of the molecular dynamics for ?-amino acids.  


The molecular dynamics of metabolites is structure dependent and vitally important for the interactive functions in their potential applications as natural materials. To understand the relationship between molecular structure and dynamics, the molecular motions of four structurally related ?-amino acids (?-alanine, ?-aminobutyric acid, 5-aminovaleric acid, and 6-aminocaproic acid) were investigated by measuring their proton spin-lattice relaxation times (T(1), T(1?)) as a function of temperature (180-440 K). (13)C CPMAS NMR and DSC analyses were performed to obtain complementary information. All of these ?-amino acids showed no phase transition in the temperature range studied but had outstandingly long proton T(1) at 300 MHz and even at 20 MHz for the deuterated forms. The molecular dynamics of all these ?-amino acids were dominated by the reorientation motions of amino groups and backbone motions except in ?-alanine. The activation energies for amino group reorientations were positively correlated with the strength of hydrogen bonds involving these groups in the crystals and the carbon-chain lengths, whereas such energies for the backbone motions were inversely correlated with the carbon-chain lengths. These findings provided essential information for the molecular dynamics of ?-amino acids and demonstrated the combined solid-state NMR methods as a useful approach for understanding the structural dependence of molecular dynamics. PMID:22251439

Huang, Jing; Zhang, Limin; Tang, Huiru



One-pot synthesis of dihydropyrimidinones using facile and reusable polyoxometalate catalysts for the Biginelli reaction  

Microsoft Academic Search

The efficiency of various heteropoly compounds as well-known solid acids is investigated for the three-component condensation reaction of an aldehyde with ?-ketoester and urea in acetonitrile to afford the dihydropyrimidinones (DHPM). Compared to the classical Biginelli reaction conditions, this new method consistently has the advantage of excellent yields and short reaction times. Furthermore, the catalyst could be easily recovered after

Razieh Fazaeli; Shahram Tangestaninejad; Hamid Aliyan; Majid Moghadam



Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures  

SciTech Connect

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.

Ojeda, Manuel; Iglesia, Enrique



Characterization of clay-based K catalysts and their application in Friedel-Crafts alkylation of aromatics  

Microsoft Academic Search

Toluene was alkylated with benzyl chloride and benzyl alcohol using a series of clays (KSF, KSF\\/0, K0, KP10, K10, KS from Süd Chemie) obtained by treating a bavarian bentonite by different acids and a Hungarian bentonite (Mád) as catalysts in a batch reactor. The catalysts were characterized by chemical analysis, thermal analysis, nitrogen adsorption, solid state nuclear magnetic resonance, X-ray

Tivadar Cseri; Sándor Békássy; François Figueras; Eleonóra Cseke; Louis-Charles de Menorval; Roger Dutartre



Anaerobic fermentation of organic solid wastes: volatile fatty acid production and separation.  


Anaerobic fermentation of organic municipal solid waste was investigated using a leach-bed reactor (LBR) to assess the volatile fatty acid (VFA) production efficiency. The leachate recycle rate in the LBR affected the VFA composition of the leachate. A six-fold increase in the recycle rate resulted in an increase of the acetic acid fraction of leachate from 24.7 to 43.0%. The separation of VFAs via leachate replacement resulted in higher total VFA production. VFA separation from synthetic VFA mix and leachate of a fermented organic waste was assessed via a counter-current flow polytetrafluoroethylene (PTFE) membrane contactor. Acetic and propionic acid permeation fluxes of 13.12 and 14.21 g/m(2).h were obtained at low feed pH values when a synthetic VFA mix was used as a feed solution. The highest selectivity was obtained for caproic acid compared to that of other VFAs when synthetic VFA mix or leachate was used as a feed solution. High pH values and the presence of suspended solids in the leachate adversely affected the permeation rate. PMID:24845331

Yesil, H; Tugtas, A E; Bayrakdar, A; Calli, B



Electrochemical performance and durability of carbon supported Pt catalyst in contact with aqueous and polymeric proton conductors.  


Significant differences in catalyst performance and durability are often observed between the use of a liquid electrolyte (e.g., sulfuric acid), and a solid polymer electrolyte (e.g., Nafion). To understand this phenomenon, we studied the electrochemical behavior of a commercially available carbon supported platinum catalyst in four different electrode structures: catalyst powder (CP), catalyst ionomer electrode (CIE), half membrane electrode assembly (HMEA), and full membrane electrode assembly (FMEA) in both ex situ and in situ experiments under a simulated start/stop cycle. We found that the catalyst performance and stability are very much influenced by the presence of the Nafion ionomers. The proton conducting phase provided by the ionomer and the self-assembled electrode structure render the catalysts a higher utilization and better stability. This is probably due to an enhanced dispersion, an improved proton-catalyst interface, the restriction of catalyst particle aggregation, and the improved stability of the ionomer phase especially after the lamination. Therefore, an innovative electrode HMEA design for ex-situ catalyst characterization is proposed. The electrode structure is identical to the one used in a real fuel cell, where the protons transport takes place solely through solid state proton conducting phase. PMID:25216270

Andersen, Shuang Ma; Skou, Eivind




SciTech Connect

An investigation was carried out of the hydrogenation and cracking of two-ring aromatic and hydroaromatic compounds catalyzed by ZnCl{sub 2} and AlCl{sub 3}. The rates of both processes are strongly affected by the Bronsted acidity of the active catalyst [e.g., H{sup +}(MX{sub n}Y){sup -}] and the Bronsted basicity of the aromatic portions of the reactant, the latter characteristic being enhanced by either methyl or hydroxyl substitution. The source of hydrogen used for hydrogenation depends on the choice of catalyst. In the presence of AlCl{sub 3}, Scholl condensation of aromatic nuclei serves as the principle source of hydrogen. Molecular hydrogen is used exclusively, though, when hydrogenation is catalyzed by ZnCl{sub 2}. The formation of reaction products and the trends in reactant reactivity are discussed on the basis of carbonium ion mechanisms.

Salim, Sadie S.; Bell, Alexis T.



Single event kinetic modeling of solid acid alkylation of isobutane with butenes over proton-exchanged Y-Zeolites  

E-print Network

Complex reaction kinetics of the solid acid alkylation of isobutane with butenes over a proton-exchanged Y-zeolite has been modeled at the elementary step level. Starting with a computer algorithm that generated the reaction network based...

Martinis Coll, Jorge Maximiliano



Gas-phase postderivatization following solid-phase microextraction for determining acidic herbicides in water.  


This study analyzes acidic herbicides from an aqueous sample by developing a methylated postderivatization on the fiber following solid-phase microextration (SPME) with diazomethane gas procedure combined with GC/MS. Analysis results indicate that a silica fiber coated with polyacrylate (PA) yields a higher extraction efficiency than that obtained with poly(dimethylsiloxane) (PDMS) using the SPME technique. Detection limits are achieved at the level of 10-30 ng/L. Linearity is obtained over a wide range, with precision below 12% RSD. In addition, the significant reduction in extraction efficiency is attributed to the concentration of humic acids exceeding 5 mg/L. Various degradation compounds of acidic herbicides in basic solution are also detected, including 2,4-dichlorophenol, 2,4,5-trichlorophenol, 4-chloro-3-methylphenol, pentachlorinated biphenyl, and tetrachlorinated biphenyl. Moreover, the amount of pentachlorinated biphenyl and tetrachlorinated biphenyl increases over time. PMID:9599589

Lee, M R; Lee, R J; Lin, Y W; Chen, C M; Hwang, B H



A modified Benesi titration procedure useful to quantify the Lewis and Bronsted sites of solid acids  

SciTech Connect

The Benesi method of acid center titration has been modified using dry box techniques so that only 1 g of sample is required to determine the strength distribution of a given sample. Addition of an excess of sterically hindered pyridine to a second 1-g sample, and subsequent titration with n-butylamine using dry box procedures, also allows the strong Lewis acid sites to be quantitatively assessed. By combination of this titration procedure with the modified Benesi procedure the number of Bronsted sites could be determined accurately. Four classes of solid acids were investigated: {gamma}-alumina, high-silica silica-alumina, fluorided alumina, and WO{sub 3} on Al{sub 2}O{sub 3}.

Murrell, L.L.; Dispenziere, N.C. Jr. (Exxon Research and Engineering Co., Annandale, NJ (USA))



Iron oxide nanoparticles immobilized to mesoporous NH2-SiO2 spheres by sulfonic acid functionalization as highly efficient catalysts.  


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

Zhang, Guoliang; Qin, Lei; Wu, Yujiao; Xu, Zehai; Guo, Xinwen



Structures of the high-temperature solid phases of the odd-numbered fatty acids from tridecanoic acid to tricosanoic acid.  


Crystal structures of the high-temperature phases of odd-numbered fatty acids (C(n)H(2n-1)OOH) from tridecanoic acid (C(13)H(25)OOH) to tricosanoic acid (C(23)H(45)OOH) are presented in this article. They have been determined from high-quality X-ray powder-diffraction patterns. Two types of high-temperature phases are adopted: one monoclinic A2/a with Z=8 for the fatty acids with n=13 and n=15, denoted as C'', and one monoclinic P2(1)/a with Z=4 for the longer-chain fatty acids, denoted as C'. It appears that the packing arrangement of the alkyl chains and of the carboxyl groups is similar in all of the structures. However, the arrangement at the methyl-group interface differs between the C' and C'' forms. A survey of the intermolecular interactions involved in these polymorphs coupled with a study of the effects of temperature on the structures have led us to a better understanding of the arrangement of the molecules within the high-temperature solid phases of odd-numbered fatty acids. PMID:17212366

Gbabode, Gabin; Negrier, Philippe; Mondieig, Denise; Moreno Calvo, Evelyn; Calvet, Teresa; Cuevas-Diarte, Miquel Angel



Characterization of vanadium oxide catalysts supported on TiO{sub 2}-ZrO{sub 2} by solid-state {sup 51}V and {sup 1}H NMR spectroscopy  

SciTech Connect

A series of TiO{sub 2}-ZrO{sub 2} mixed oxide supported vanadia catalysts with various V{sub 2}O{sub 5} loadings ranging from 1 to 16 wt % were prepared by a wet impregnation method and were characterized by means of solid-state {sup 51}V and {sup 1}H NMR spectroscopic techniques. The solid-state {sup 51}V NMR spectra of V{sub 2}O{sub 5}/TiO{sub 2}-ZrO{sub 2} catalysts reveal the existence of two types of dispersed surface vanadium oxide complexes in a tetrahedral oxygen environment at lower vanadium loadings adn a third three-dimensional crystalline V{sub 2}O{sub 5} in distorted octahedral environment at higher vanadium contents. The proton NMR results provide evidence for the existence of metal oxide support interaction through the support hydroxyl groups. 33 regs., 4 figs.

Reddy, B.M.; Reddy, E.P.; Srinivas, S.T. [Indian Inst. of Chemical Technology, Hyderabad (India)] [and others



Coke-free direct formic acid solid oxide fuel cells operating at intermediate temperatures  

NASA Astrophysics Data System (ADS)

Formic acid is investigated as a fuel for Solid Oxide Fuel Cells (SOFCs) for the first time. Thermodynamic calculations demonstrate that carbon deposition is avoidable above 600 °C. The carbon deposition properties are also investigated experimentally by first treating a nickel plus yttria-stabilized zirconia (Ni-YSZ) anode material in particle form under a formic acid-containing atmosphere for a limited time at 500-800 °C and then analyzing the particles by O2-TPO. This analysis confirms that carbon deposition on Ni-YSZ is weak above 600 °C. We further treat half-cells composed of YSZ electrolyte and Ni-YSZ anode under formic acid-containing atmosphere at 600, 700 and 800 °C; the anodes maintain their original geometric shape and microstructure and show no obvious weight gain. It suggests that formic acid can be directly fed into SOFCs constructed with conventional nickel-based cermet anodes. I-V tests show that the cell delivers a promising peak power density of 571 mW cm-2 at 800 °C. In addition, the cells also show good performance stability. The results indicate that formic acid is highly promising as a direct fuel for SOFCs without the need for cell material modifications.

Chen, Yubo; Su, Chao; Zheng, Tao; Shao, Zongping



Amino acid/KI as multi-functional synergistic catalysts for cyclic carbonate synthesis from CO2 under mild reaction conditions: a DFT corroborated study.  


Naturally occurring amino acids were identified as efficient co-catalysts for the alkali metal halide-mediated synthesis of cyclic carbonates from carbon dioxide and epoxides under mild, solvent free reaction conditions. The binary system of histidine/potassium iodide gave an appreciable turnover number of 535 for propylene oxide in 3 h. Detailed studies evaluating a variety of amino acids revealed that the basic amino acids afforded better conversion rates. The formation of a seven membered ring involving the zwitterionic ends of the amino acid, the metal halide, and the epoxide was considered to accelerate the catalysis rate. Density functional theory calculations were performed for the first time on amino acid co-catalyzed cycloaddition to provide further evidence for this hypothesis. The iodide ions of the alkali metal halide displayed excellent synergism with the hydrogen bonding groups of the amino acids in the production of cyclic carbonates, whereas bromide and chloride anions functioned less efficiently. The utilization of amino acids to enhance the catalytic activity of the cheap and eco-friendly alkali metal halides for cyclic carbonate synthesis represents a cost-effective, greener route towards the chemical fixation of carbon dioxide. PMID:24270098

Roshan, Kuruppathparambil Roshith; Kathalikkattil, Amal Cherian; Tharun, Jose; Kim, Dong Woo; Won, Yong Sun; Park, Dae Won



Regeneration of three-way automobile catalysts using biodegradable metal chelating agent--S, S-ethylenediamine disuccinic acid (S, S-EDDS).  


Regeneration of the activity of three-way catalytic converters (TWCs) was tested for the first time using a biodegradable metal chelating agent (S, S-ethylenediamine disuccinic acid (S, S-EDDS). The efficiency of this novel environmentally friendly solvent in removing various contaminants such as P, Zn, Pb, Cu and S from commercial aged three-way catalysts, and improving their catalytic performance towards CO and NO pollutants removal has been investigated. Four samples of catalysts from the front and rear inlets of two different TWCs with different mileages and aged under completely different driving conditions were investigated. The catalysts were characterized using various techniques, such as X-ray diffraction (XRD), Scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area measurements (N(2) adsorption at 77 K). Quantitative ICP-MS analyses and SEM-EDS studies show the removal of Zn, P and Pb. SEM-EDS images obtained at low magnification (50 ?m) showed considerable differences in the surface morphology and composition after washing with S, S-EDDS. However, XRD studies indicated neither little to no removal of major contaminant compound phases nor major structural changes due to washing. Correspondingly, little or no enhancement in BET surface area was observed between the used and washed samples. Light-off curves show that the regeneration procedure employed can effectively improve the catalytic performance towards NO pollutant. PMID:21177030

Subramanian, B; Christou, S Y; Efstathiou, A M; Namboodiri, V; Dionysiou, D D



SolidPhase Organic Synthesis of Vinyl-Substituted 1,3,4-Oxadiazoles Using Polymer-Bound ?-Selenopropionic Acid  

Microsoft Academic Search

Vinyl-substituted 1,3,4-oxadiazoles can be efficiently synthesized through acylation, cyclocondensation, and oxidation–elimination reaction from polystyrene-supported ?-selenopropionic acid and acid hydrazides. This new solid-phase organic synthesis method could provide the target compounds in good yield and purity, with advantages of decreased volatility and simplification of workup procedure.

Gui-Yun Fu; Shou-Ri Sheng; Xiao-Ling Liu; Ming-Zhong Cai; Xian Huang



Kinetic resolution of racemic 2-hydroxy-?-butyrolactones by asymmetric esterification using diphenylacetic acid with pivalic anhydride and a chiral acyl-transfer catalyst.  


Various optically active 2-hydroxy-?-butyrolactone derivatives are produced via the kinetic resolution of racemic 2-hydroxy-?-butyrolactones with diphenylacetic acid using pivalic anhydride and (R)-benzotetramisole ((R)-BTM), a chiral acyl-transfer catalyst. Importantly, the substrate scope of this novel protocol is fairly broad (12 examples, s-value; up to over 1000). In addition, we succeeded in disclosing the reaction mechanism to afford high enantioselectivity using theoretical calculations and expounded on the substituent effects at the C-3 positions in 2-hydroxylactones. PMID:23461674

Nakata, Kenya; Gotoh, Kouya; Ono, Keisuke; Futami, Kengo; Shiina, Isamu



Solid-state NMR studies of theophylline co-crystals with dicarboxylic acids.  


In this work, three polycrystalline materials containing co-crystals of theophylline with malonic, maleic, and glutaric acids were studied using (13)C, (15)N and (1)H solid-state NMR and FT-IR spectroscopy. The NMR assignments were supported by gauge including projector augmented waves (GIPAW) calculations of chemical shielding, performed using X-ray determined geometry. The experimental (13)C cross polarization/magic angle spinning (CP/MAS) NMR results and the calculated isotropic chemical shifts were in excellent agreement. A rapid and convenient method for theophylline co-crystals crystal structure analysis has been proposed for co-crystals, which are potentially new APIs. PMID:25194346

Pindelska, Edyta; Sokal, Agnieszka; Szeleszczuk, Lukasz; Pisklak, Dariusz Maciej; Kolodziejski, Waclaw



Light-induced, site-selective isomerization of glyoxylic acid in solid xenon  

NASA Astrophysics Data System (ADS)

The isomerization of glyoxylic acid (GA) and its water complex was studied in a low temperature xenon matrix. The aim of these studies was to understand how xenon environment affects the cis-trans GA interconversion upon near infrared irradiation. In solid xenon, the GA conformers are embedded in two different matrix sites. These show up as different vibrational bands of GA that exhibit different kinetic rates of isomerization. Upon complexation with water, the isomerization process slows down. Xenon matrix appears not to affect energy relaxation process via intramolecular or intermolecular hydrogen bond as compared with previous experiments in an argon.

Olbert-Majkut, Adriana; Wierzejewska, Maria; Lundell, Jan



Determination of the mean solid-liquid interface energy of pivalic acid  

NASA Technical Reports Server (NTRS)

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.

Singh, N. B.; Gliksman, M. E.



Recovery of Alkylation Activity in Deactivated USY Catalyst Using Supercritical Fluids: A Comparison of Light Hydrocarbons  

SciTech Connect

Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical fluids (SCF). 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 fluids over the catalyst bed. A comparison of reactivation fluids on catalyst activity recovery is reported. Fluids examined included helium, propane, n-butane, isobutane, n-pentane, and isopentane. Phases studied included gas, liquid, and supercritical. As much as 82% of the fresh catalyst activity was recovered when employing supercritical isobutane. The ability of the fluid to facilitate a hydride reaction with the adsorbed deactivating high-molecular weight carbocations was indicated as an important property necessary to attain high levels of catalyst activity recovery. Activity recovery utilizing supercritical fluids that enhance reactivation by both reacting with and desorbing fouling compounds appears to be a promising technique to advance solid catalyst alkylation.

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



In situ controlled promotion of catalyst surfaces via solid electrolytes: Ethylene oxidation on Rh and propylene oxidation on Pt  

Microsoft Academic Search

The kinetics of C2H4 oxidation on Rh and C3H6 oxidation on Pt were investigated on polycrystalline metal films interfaced with ZrO2(8mol%Y2O3) solid electrolyte in galvanic cells of the type:\\u000a \\u000a \\u000a \\u000a \\u000a $$\\\\begin{gathered} C_2 H_4 ,O_2 ,Rh\\/YSZ\\/Pt,O_2 and \\\\hfill \\\\\\\\ C_3 H_6 ,O_2 ,CO_2 ,Pt\\/YSZ\\/Au,C_3 H_6 ,O_2 ,CO_2 \\\\hfill \\\\\\\\ \\\\end{gathered} $$\\u000a \\u000a \\u000a \\u000a \\u000a \\u000a It was found that by applying positive potentials and thus, supplying

A. C. Kaloyannis; C. A. Pliangos; I. V. Yentekakis; C. G. Vayenas



Optimization of Citric Acid Production from a New Strain and Mutant of Aspergillus niger Using Solid State Fermentation  

Microsoft Academic Search

A new strain of Aspergillus niger isolated from soil and its mutant were used for citric acid production from carob under solid-state fermentation conditions. The parental strain produced 30 g\\/kg citric acid, while the mutant G4, selected after four rounds of gamma ray irradiation, produced 60 g\\/kg. Maximum citric acid production was obtained after 7 days of incubation, as the

Faiez Alani; Murray Moo-Young; William Anderson; Zakaria Bataine



pKa Modulation of the Acid/Base Catalyst within GH32 and GH68: A Role in Substrate/Inhibitor Specificity?  

PubMed Central

Glycoside hydrolases of families 32 (GH32) and 68 (GH68) belong to clan GH-J, containing hydrolytic enzymes (sucrose/fructans as donor substrates) and fructosyltransferases (sucrose/fructans as donor and acceptor substrates). In GH32 members, some of the sugar substrates can also function as inhibitors, this regulatory aspect further adding to the complexity in enzyme functionalities within this family. Although 3D structural information becomes increasingly available within this clan and huge progress has been made on structure-function relationships, it is not clear why some sugars bind as inhibitors without being catalyzed. Conserved aspartate and glutamate residues are well known to act as nucleophile and acid/bases within this clan. Based on the available 3D structures of enzymes and enzyme-ligand complexes as well as docking simulations, we calculated the pKa of the acid-base before and after substrate binding. The obtained results strongly suggest that most GH-J members show an acid-base catalyst that is not sufficiently protonated before ligand entrance, while the acid-base can be fully protonated when a substrate, but not an inhibitor, enters the catalytic pocket. This provides a new mechanistic insight aiming at understanding the complex substrate and inhibitor specificities observed within the GH-J clan. Moreover, besides the effect of substrate entrance on its own, we strongly suggest that a highly conserved arginine residue (in the RDP motif) rather than the previously proposed Tyr motif (not conserved) provides the proton to increase the pKa of the acid-base catalyst. PMID:22662155

Yuan, Shuguang; Le Roy, Katrien; Venken, Tom; Lammens, Willem; Van den Ende, Wim; De Maeyer, Marc



Catalysts for emerging energy applications  

SciTech Connect

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.

Bruce C. Gates; George W. Huber; Christopher L. Marshall; Phillip N. Ross; Jeffrey Siirola; Yong Wang [University of California-Davis, CA (United States)



Influence of solid-state acidity on the decomposition of sucrose in amorphous systems II (effect of buffer).  


It was of interest to investigate the solid-state acidity using indicator probe molecules and sucrose degradation. Amorphous samples containing lactose, sucrose, buffers (citrate, malate, tartarate, or phosphate) with different pH values, and sodium chloride (to adjust the ionic strength) were prepared by freeze-drying. The lyophiles were characterized using powder X-ray diffraction, differential scanning calorimetry, and Karl Fischer titrimetry. The solid-state acidity of all lyophiles was measured using diffuse reflectance spectroscopy and suitable indicators (thymol blue or bromophenol blue). Selected lyophiles were subjected to a temperature of 60 degrees C and were analyzed for sucrose degradation using the Trinder kit. The results obtained from this study have shown that good correlation can be obtained between the solid-state acidity and the molar ratio of the salt and the acid in solution. The degradation of sucrose in the lyophiles is extremely sensitive to the solid-state acidity and might be able to provide a better estimate for the acidity than the indicator probe molecules. The Hammett acidity-rate profile for sucrose degradation in the lyophiles (using four different buffers) was also obtained. The profile showed similarity to the pH-rate profile in solution, and no buffer catalysis for sucrose degradation was detected in this study. PMID:19016102

Alkhamis, Khouloud A



Catalysts and method  


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.

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



Far infrared spectra of solid state aliphatic amino acids in different protonation states.  


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. PMID:20331320

Trivella, Aurélien; Gaillard, Thomas; Stote, Roland H; Hellwig, Petra



Preparation of glycosylated amino acids suitable for Fmoc solid-phase assembly.  


Many biological interactions and functions are mediated by glycans, consequently leading to the emerging importance of carbohydrate and glycoconjugate chemistry in the design of novel drug therapeutics. Despite the challenges that carbohydrate moieties bring into the synthesis of glycopeptides and glycoproteins, considerable progress has been made during recent decades. Glycopeptides carrying many simple glycans have been chemically synthesized, enzymatic approaches have been utilized to introduce more complex glycans, and most recently native chemical ligation has enabled synthesis of glycoproteins from well-designed peptide and glycopeptide building blocks. Currently, general synthetic methodology for glycopeptides relies on preformed glycosylated amino acids for the stepwise solid-phase peptide synthesis. The formation of glycosidic bonds is of fundamental importance in the assembly of glycopeptides. As such, every glycosylation has to be regarded as a unique problem, demanding considerable systematic research. In this chapter we will summarize the most common chemical methods for the stereoselective synthesis of N- and O-glycosylated amino acids. The particular emphasis will be given to the preparation of building blocks for use in solid-phase glycopeptide synthesis based on the 9-fluorenylmethoxycarbonyl (Fmoc) protective group strategy. PMID:18726575

Cudic, Mare; Burstein, Gayle D



An Efficient One-Pot Green Protocol for the Synthesis of 5-Unsubstituted 3,4-Dihydropyrimidin-2(1H)-Ones Using Recyclable Amberlyst 15 DRY as a Heterogeneous Catalyst via Three-Component Biginelli-Like Reaction  

PubMed Central

An environmentally benign green protocol for the synthesis of 5-unsubstituted 3,4-dihydropyrimidin-2(1H)-ones using Amberlyst 15 DRY as a recyclable catalyst has been developed. The use of resinous, nontoxic, thermally stable, and inexpensive Amberlyst 15 DRY, as a recyclable heterogeneous catalyst, makes the process simple with negligible chemical waste. Among the various solid acid catalysts Amberlyst 15 DRY was found to be the most efficient catalyst with regard to reaction time, yield, and ease of work-up procedure. PMID:24052845

Jetti, Srinivasa Rao; Verma, Divya; Jain, Shubha



An Efficient One-Pot Green Protocol for the Synthesis of 5-Unsubstituted 3,4-Dihydropyrimidin-2(1H)-Ones Using Recyclable Amberlyst 15 DRY as a Heterogeneous Catalyst via Three-Component Biginelli-Like Reaction.  


An environmentally benign green protocol for the synthesis of 5-unsubstituted 3,4-dihydropyrimidin-2(1H)-ones using Amberlyst 15 DRY as a recyclable catalyst has been developed. The use of resinous, nontoxic, thermally stable, and inexpensive Amberlyst 15 DRY, as a recyclable heterogeneous catalyst, makes the process simple with negligible chemical waste. Among the various solid acid catalysts Amberlyst 15 DRY was found to be the most efficient catalyst with regard to reaction time, yield, and ease of work-up procedure. PMID:24052845

Jetti, Srinivasa Rao; Verma, Divya; Jain, Shubha



Reuse of sewage sludge as a catalyst in ozonation--efficiency for the removal of oxalic acid and the control of bromate formation.  


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

Wen, Gang; Pan, Zhi-Hui; Ma, Jun; Liu, Zheng-Qian; Zhao, Lei; Li, Jun-Jing



Phosphomolybdic and phosphotungstic acids as efficient catalysts for the synthesis of bridged 1,2,4,5-tetraoxanes from ?-diketones and hydrogen peroxide.  


Phosphomolybdic acid (PMA) and phosphotungstic acid (PTA) efficiently catalyze the addition of H2O2 to ?-diketones to form bridged 1,2,4,5-tetraoxanes. These reactions are not accompanied by the formation of monocyclic peroxides containing hydroxy and hydroperoxide groups or polymeric peroxides. The use of these catalysts made it possible to obtain bridged tetraoxanes from easily oxidizable benzoylacetone derivatives and ?-unsubstituted ?-diketones. The syntheses are scaled up to ten grams. The resulting peroxides can be easily isolated from the reaction mixture by column chromatography. The yield of tetraoxanes depends on the structure of ?-diketone and varies from 12 to 83%. NMR monitoring of two bridged 1,2,4,5-tetraoxanes synthesis was carried out. PMID:23446630

Terent'ev, Alexander O; Yaremenko, Ivan A; Vil', Vera A; Moiseev, Igor K; Kon'kov, Sergey A; Dembitsky, Valery M; Levitsky, Dmitri O; Nikishin, Gennady I



Electron-Withdrawing Trifluoromethyl Groups in Combination with Hydrogen Bonds in Polyols: Brønsted Acids, Hydrogen-Bond Catalysts, and Anion Receptors  

SciTech Connect

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.

Shokri, Alireza; Wang, Xue B.; Kass, Steven R.



Potential effects of clean coal technologies on acid precipitation, greenhouse gases, and solid waste disposal  

SciTech Connect

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.

Blasing, T.J.; Miller, R.L.; McCold, L.N.



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

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

Ravi, K.; Krishnakumar, B.; Swaminathan, M.



Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making  


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.

Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA



Bioleaching of spent fluid catalytic cracking catalyst using Aspergillus niger  

Microsoft Academic Search

The use of the fungus Aspergillus niger for the bioleaching of heavy metals from spent catalyst was investigated, with fluid catalytic cracking (FCC) catalyst as a model. Bioleaching was examined in batch cultures with the spent catalysts at various pulp densities (1–12%). Chemical leaching was also performed using mineral acids (sulphuric and nitric acids) and organic acids (citric, oxalic and

Khin Moh Moh Aung; Yen-Peng Ting



Incorporating Amino Acid Esters into Catalysts for Hydrogen Oxidation: Steric and Electronic Effects and the Role of Water as a Base  

SciTech Connect

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.

Lense, Sheri; Ho, Ming-Hsun; Chen, Shentan; Jain, Avijita; Raugei, Simone; Linehan, John C.; Roberts, John A.; Appel, Aaron M.; Shaw, Wendy J.



Natural DNA-modified graphene/Pd nanoparticles as highly active catalyst for formic acid electro-oxidation and for the Suzuki reaction.  


Natural DNA has been considered as a building block for developing novel functional materials. It is abundant, renewable, and biodegradable and has a well-defined structure and conformation with many unique features, which are difficult to find in other polymers. Herein, calf thymus DNA modified graphene/Pd nanoparticle (DNA-G-Pd) hybrid materials are constructed for the first time using DNA as a mediator, and the prepared DNA-G-Pd hybrid shows high catalytic activity for fuel cell formic acid electro-oxidation and for organic Suzuki reaction. The main advantages of using DNA are not only because the aromatic nucleobases in DNA can interact through ?-? stacking with graphene basal surface but also because they can chelate Pd via dative bonding in such defined sites along the DNA lattice. Our results indicate that isolated, homogeneous, and ultrafine spherical Pd nanoparticles are densely in situ decorated on DNA-modified graphene surfaces with high stability and dispersibility. The prepared DNA-G-Pd hybrid has much greater activity and durability for formic acid electro-oxidation than the commercial Pd/C catalyst and polyvinylpyrrolidone-mediated graphene/Pd nanoparticle (PVP-G-Pd) hybrid used for direct formic acid fuel cells (DFAFCs). Besides, the DNA-G-Pd hybrid can also be an efficient and recyclable catalyst for the organic Suzuki reaction in aqueous solution under aerobic conditions without any preactivation. Since DNA can chelate various transition metal cations, this proof-of-concept protocol provides the possibility for the tailored design of other novel catalytic materials based on graphene with full exploitation of their properties. PMID:22973944

Qu, Konggang; Wu, Li; Ren, Jinsong; Qu, Xiaogang




NSDL National Science Digital Library

Findingsurface area and volume of solids. These sites a have drills for learning surface area and volume, Volume of Rec. Prism Surface Area This site allows you to change the surface area and volume of a prism. This site allows you to change the surface area and volume of a prism. This site has a quiz for you to do. Quiz Geodesic domes Geodesic domes ...




Preparation and characterization of ascorbic acid loaded solid lipid nanoparticles and investigation of their apoptotic effects.  


In this paper, ascorbic acid (Vitamin C, AA) known as an antioxidant was successfully incorporated in solid lipid nanoparticles (SLNs) by hot homogenization and efficient delivery of AA to cancer cells. The obtained SLN formulations were characterized by Nano Zetasizer ZS and HPLC with the particle size being less than 250nm. AA-SLNs exhibited sustained release and high entrapment efficiency. According to MTT test results, AA-SLNs showed high cytotoxic activity compared to the free AA against H-Ras 5RP7 cells without damaging NIH/3T3 control cells. These results were supported by the Annexin V-PI and caspase-3 assay. Furthermore, as compared to the AA, AA-SLNs exhibited more efficient cellular uptake, accumulated in the cytoplasm and induced apoptosis which was observed by confocal laser scanning microscopy (CLSM) and transmission electron microscopy (TEM). Thus, the results of this study suggest that SLNs can be a potential nanocarrier system for AA. PMID:24985762

Güney, Gamze; Kutlu, H Mehtap; Genç, Lütfi



Microwave Effect for Glycosylation Promoted by Solid Super Acid in Supercritical Carbon Dioxide  

PubMed Central

The effects of microwave irradiation (2.45 GHz, 200 W) on glycosylation promoted by a solid super acid in supercritical carbon dioxide was investigated with particular attention paid to the structure of the acceptor substrate. Because of the symmetrical structure and high diffusive property of supercritical carbon dioxide, microwave irradiation did not alter the temperature of the reaction solution, but enhanced reaction yield when aliphatic acceptors are employed. Interestingly, the use of a phenolic acceptor under the same reaction conditions did not show these promoting effects due to microwave irradiation. In the case of aliphatic diol acceptors, the yield seemed to be dependent on the symmetrical properties of the acceptors. The results suggest that microwave irradiation do not affect the reactivity of the donor nor promoter independently. We conclude that the effect of acceptor structure on glycosylation yield is due to electric delocalization of hydroxyl group and dielectrically symmetric structure of whole molecule. PMID:20054471

Hinou, Hiroshi; Saito, Naohiro; Ogawa, Masato; Maeda, Takahiko; Nishimura, Shin-Ichiro



Experimental and computational thermochemical study and solid-phase structure of 5,5-dimethylbarbituric acid.  


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

Roux, María Victoria; Notario, Rafael; Foces-Foces, Concepción; Temprado, Manuel; Ros, Francisco; Emel'yanenko, Vladimir N; Verevkin, Sergey P



Chemical Interactions in Multimetal/Zeolite Catalysts  

SciTech Connect

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.

Sachtler, Wolfgang M. H.



Treatment of acid mine drainage with anaerobic solid-substrate reactors  

SciTech Connect

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.

Drury, W.J.



Enhancement of alkylation catalysts for improved supercritical fluid regeneration  


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.

Ginosar, Daniel M. (Idaho Falls, ID); Petkovic, Lucia M. (Idaho Falls, ID)



Molecular water oxidation catalyst  


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.

Gratzel, Michael (St. Sulpice, CH); Munavalli, Shekhar (Bel Air, MD); Pern, Fu-Jann (Lakewood, CO); Frank, Arthur J. (Lakewood, CO)



Solid-Supported Hydrazone of 4-(4'-Formyl-3'-methoxyphenoxy)butyric Acid As a New Traceless Linker for Solid-Phase Synthesis.  


The use of a hydrazine derived from a backbone amide linker as a new hydrazone-based traceless linker for solid-phase organic synthesis is described. The stability of the linker was tested under various conditions, including treatment with acids, bases, and borohydrides. Final compounds can be released by selective cleavage using trimethylsilanolate. To demonstrate the versatility of the linker, the synthesis of a model compound under various reaction conditions was performed with good results. PMID:25536078

Okorochenkov, Sergei; Burglova, Kristyna; Popa, Igor; Hlavac, Jan



Hydrocarbon synthesis catalyst and method of preparation  


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.

Sapienza, Richard S. (Shoreham, NY); Sansone, Michael J. (Summit, NJ); Slegeir, William A. R. (Hampton Bays, NY)



Hydrocarbon synthesis catalyst and method of preparation  


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.

Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.



Effect of organic acids and nano-sized ceramic doping on PEO-based solid polymer electrolytes  

Microsoft Academic Search

Composite solid polymer electrolytes (CSPEs) consisting of polyethyleneoxide (PEO), LiClO4, organic acids (malonic, maleic, and carboxylic acids), and\\/or Al2O3 were prepared in acetonitrile. CSPEs were characterized by Brewster Angle Microscopy (BAM), thermal analysis, ac impedance, cyclic voltammetry, and tested for charge–discharge capacity with the Li or LiNi0.5Co0.5O2 electrodes coated on stainless steel (SS). The morphologies of the CSPE films were

Jae Won Park; Euh Duck Jeong; Mi-Sook Won; Yoon-Bo Shim



A QM/MM study of Kemptide phosphorylation catalyzed by protein kinase A. The role of Asp166 as a general acid/base catalyst.  


In this work a theoretical study of the ?-phosphoryl group transfer from ATP to Ser17 of the synthetic substrate Kemptide (LRRASLG) in protein kinase A (PKA) has been carried out with a solvated model of the PKA-Mg2ATP-Kemptide system based on the X-ray crystallographic structure. We have used high levels (B3LYP/MM and MP2/MM) of theory to determine the overall reaction paths of the so-called concerted loose mechanism trying to clarify some aspects of that mechanism still under debate. Our calculations demonstrate for the first time in a complete model of the ternary system the viability of the final step of the catalytic mechanism in which the protonation of the phosphokemptide product by Asp166 takes place. Asp166 is a base catalyst that abstracts the H?Ser17 of Kemptide thus facilitating the phosphoryl transfer, but it also acts as an acid catalyst by donating the proton just accepted from Ser17 to the O2?ATP atom of the phosphoryl group. PMID:25535906

Pérez-Gallegos, Ayax; Garcia-Viloca, Mireia; González-Lafont, Àngels; Lluch, José M



Supported molten-metal catalysts  


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 (< 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.

Datta, Ravindra (Iowa City, IA); Singh, Ajeet (Iowa City, IA); Halasz, Istvan (Iowa City, IA); Serban, Manuela (Iowa City, IA)



Formulation of curcumin-loaded solid lipid nanoparticles produced by fatty acids coacervation technique.  


Curcumin (CU) loaded solid lipid nanoparticles (SLNs) of fatty acids (FA) were prepared with a coacervation technique based on FA precipitation from their sodium salt micelles in the presence of polymeric non-ionic surfactants. Myristic, palmitic, stearic, and behenic acids, and different polymers with various molecular weights and hydrolysis grades were employed as lipid matrixes and stabilisers, respectively. Generally, spherical-shaped nanoparticles with mean diameters below 500?nm were obtained, and using only middle-high hydrolysis, grade-polymer SLNs with diameters lower than 300?nm were produced. CU encapsulation efficiency was in the range 28-81% and highly influenced by both FA and polymer type. Chitosan hydrochloride was added to FA SLN formulations to produce bioadhesive, positively charged nanoparticles. A CU-chitosan complex formation could be hypothesised by DSC analysis, UV-vis spectra and chitosan surface tension determination. A preliminary study on HCT-116 colon cancer cells was developed to evaluate the influence of CU-loaded FA SLNs on cell viability. PMID:21702702

Chirio, Daniela; Gallarate, Marina; Peira, Elena; Battaglia, Luigi; Serpe, Loredana; Trotta, Michele



[Solid phase isotope exchange with spillover hydrogen in amino acids, peptides, and proteins].  


We summarize here information on the theoretical and experimental study of high-temperature (150-200 degrees C) solid phase catalytic isotope exchange (HTSPCIE) carried out with amino acids, peptides, and proteins under the action of spillover hydrogen. Main specific features of the HTSPCIE reaction, its mechanism, and its use for studying spatial interactions in polypeptides are discussed. A virtually complete absence of racemization makes this reaction a valuable preparative method. The main regularities of the HTSPCIE reaction with the participation of spillover tritium have been revealed in the case of peptides and proteins, and the dependence of reactivity of peptide fragments on the spatial organization of their molecules has been studied. An important peculiarity of this reaction is that HTSPCIE proceeds at 150-200 degrees C with a high degree of chirality retention in amino acids and peptides. This is provided by its reaction mechanism, which consists in a synchronous one-center substitution at the saturated carbon atom characterized by the formation of pentacoordinated carbon and a three-center bond between the carbon and the incoming and outgoing hydrogen atoms. PMID:15787209

Zolotarev, Iu A; Dadaian, A K; Borisov, Iu A



Synthesis of 3,4-Dihydropyrimidin-2(1H)-Ones and Their Corresponding 2(1H)Thiones Using Trichloroacetic Acid as a Catalyst under Solvent-Free Conditions  

PubMed Central

Trichloroacetic acid was found to be a convenient catalyst for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones and their corresponding 2(1H)-thiones through a one-pot three-component reaction of aldehydes, alkyl acetoacetate, and urea or thiourea at 70°C under solvent-free conditions. PMID:24052844

Karimi-Jaberi, Zahed; Moaddeli, Mohammad Sadegh



Melamine trisulfonic acid: A new, efficient and recyclable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1 H)-ones\\/thiones in the absence of solvent  

Microsoft Academic Search

Melamine trisulfonic acid (MTSA) can be used as an efficient and recyclable catalyst for the promotion of the synthesis of 3,4-dihydropyrimidin-2(1H)-ones\\/thiones (DHPMs) in the absence of solvent. All reactions were performed at 80°C in good to high yields.

Farhad Shirini; Mohammad Ali Zolfigol; Jalal Albadi



GaAlCl x -grafted Mont.K-10 clay: Highly active and stable solid catalyst for the Friedel-Crafts type benzylation and acylation reactions  

Microsoft Academic Search

A liquid phase reaction of anhydrous GaCl3 and AlCl3 with the surface hydroxyl groups (with HCl evolution) of Mont.K-10 clay in dry CCL4 under reflux resulted in a novel GaAlClx-grafted Mont.K-10 catalyst [with Cl\\/(Ga+Al)=1]. The catalyst showed high activity and stability in the Freidel-Crafts type benzylation and benzoylation (by benzyl chloride and benzoyl chloride, respectively) of benzene, naphthalene and substituted

Vasant R. Choudhary; Rani Jha



Solvent-washable polymer templated synthesis of mesoporous materials and solid-acid nanocatalysts in one-potw  

E-print Network

was also a significant advance in the field of mesoporous materials chemistry.2 The SBA15 material allowsSolvent-washable polymer templated synthesis of mesoporous materials and solid-acid nanocatalysts the inorganic material, surfactant template, and synthetic conditions employed, mesoporous materials with widely

Schiff, Eric A.


10th International Conference on Chemometrics in Analytical Chemistry OP35 Simultaneuosly Calibrating Solids, Sugars and Acidity of Tomato  

E-print Network

Calibrating Solids, Sugars and Acidity of Tomato Products Using PLS2 and NIR Spectroscopy André M. K. Pedro* 1, multivariate calibration, tomato quality The purpose of this work is to develop a robust calibration model for determining, simultaneously and non-destructively, relevant quality parameters in processed tomato products

Ferreira, Márcia M. C.



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...


Bimetallic Catalysts.  

ERIC Educational Resources Information Center

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…

Sinfelt, John H.



The conversion of CO2 and CH4 to acetic acid over the Au-exchanged ZSM-5 catalyst: a density functional theory study.  


The direct conversion of methane and carbon dioxide to acetic acid is one of the most challenging research topics. Using the density functional theory (M06-L) the study reveals the catalytic activity of the Au(I)-ZSM-5 zeolite in this reaction. The Au(I)-ZSM-5 is represented by a 34T quantum cluster model. The activation of the C-H bond over the Au-ZSM-5 zeolite would readily take place via the homolytic ?-bond activation with an energy barrier of 10.5 kcal mol(-1), and subsequent proton transfer from the Au cation to the zeolitic oxygen, yielding the stable methyl-gold complex adsorbed on the zeolite Brønsted acid. The conversion of CO(2) on this bi-functional catalyst involves the Brønsted acid site playing a role in the protonation of CO(2) and the methyl-gold complex acting as a methylating agent. The activation energy of 52.9 kcal mol(-1) is predicted. PMID:22903398

Panjan, Wasinee; Sirijaraensre, Jakkapan; Warakulwit, Chompunuch; Pantu, Piboon; Limtrakul, Jumras



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.  


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

Fukushima, Masami; Shigematsu, Satoko; Nagao, Seiya



Preparation of fibrous titania oxynitride - carbon catalyst and oxygen reduction reaction analysis in both acidic and alkaline media  

NASA Astrophysics Data System (ADS)

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.

Kinumoto, Taro; Sou, Yoshinori; Ono, Kohei; Matsuoka, Miki; Arai, Yasuhiko; Tsumura, Tomoki; Toyoda, Masahiro



The use of supported acidic ionic liquids in organic synthesis.  


Catalysts obtained by the immobilisation of acidic ionic liquids (ILs) on solid supports offer several advantages compared to the use of catalytically active ILs themselves. Immobilisation may result in an increase in the number of accessible active sites of the catalyst and a reduction of the amount of the IL required. The ionic liquid films on the carrier surfaces provide a homogeneous environment for catalytic reactions but the catalyst appears macroscopically as a dry solid, so it can simply be separated from the reaction mixture. As another advantage, it can easily be applied in a continuous fixed bed reactor. In the present review the main synthetic strategies towards the preparation of supported Lewis acidic and Brønsted acidic ILs are summarised. The most important characterisation methods and structural features of the supported ionic liquids are presented. Their efficiency in catalytic reactions is discussed with special emphasis on their recyclability. PMID:24972271

Skoda-Földes, Rita



Composite catalyst for hydrocarbon conversion reactions  

SciTech Connect

A catalyst composite is described comprising a perfluorinated-polymersulfonic acid and an ion-stabilizing agent selected from the group consisting of C/sub 2/-C/sub 6/ fluorinated carboxylic acids and alcohols.

Farocasiu, D.



Enzymatic hydrolysis and succinic acid fermentation from steam-exploded corn stalk at high solid concentration by recombinant Escherichia coli.  


Steam-exploded corn stalk biomass was used as the substrate for succinic acid production via lignocellulose enzymatic hydrolysis and fermentation. Succinic acid fermentation was investigated in Escherichia coli strains overexpressing cyanobacterium Anabaena sp. 7120 ecaA gene encoding carbonic anhydrase (CA). For the washed steam-exploded corn stalk at 30 % substrate concentration, i.e., 30 % water-insoluble solids (WIS), enzymatic hydrolysis yielded 97.5 g/l glucose solution and a cellulose conversion of 73.6 %, thus a high succinic acid level up to 38.6 g/l. With the unwashed steam-exploded corn stalk, though a cellulose conversion of 71.2 % was obtained in hydrolysis at 30 % solid concentration (27.9 % WIS), its hydrolysate did not ferment at all, and the hydrolysate of 25 % solid loading containing 3.8 g/l acetic acid and 168.2 mg/l furfural exerted a strong inhibition on succinic acid production. PMID:23797507

Wu, Dexi; Li, Qiang; Wang, Dan; Dong, Yugang



Multiple headspace solid-phase microextraction for quantifying volatile free fatty acids in cheeses.  


Multiple headspace solid-phase microextraction (MHS-SPME) has been utilized for the quantitative determination of 9 volatile free fatty acids (FFAs) in cheeses, in combination with gas-chromatography and flame-ionization detection (GC-FID). Variables affecting HS-SPME and MHS-SPME were optimized to attain adequate sensitivity while allowing correct application of the MHS method. Thus, the MHS-SPME method was successfully performed when using 0.3g of cheese and 1 mL of NaCl (sat. solution), which is subjected to four consecutive extractions using the carboxen-polydimethylsyloxane (CAR-PDMS) as the commercial SPME coating, 40 min of HS extraction time at 45°C, and 6 min of desorption time in the GC injector at 290°C. The MHS-SPME permitted the calculation of ? values, which range from 0.72±0.01-0.95±0.02, depending on the cheese studied. Later, this ? parameter is used to perform quantitation for the 9 volatile FFAs after just a single HS-SPME extraction, using an external solvent calibration curve. The validity of the utilization of an external solvent calibration was tested with aqueous standards of volatile FFAs, getting average recoveries higher than 81.2%. Quantitation by MHS-SPME was free of matrix interferences despite measuring a complex cheese sample. The optimized method was validated, presenting inter-day reproducibility values (as RSD in %) lower than 13%, and limits of detection down to 7 µg kg(-1). The method was also compared with a conventional extraction method such as solid-phase extraction for the studied cheeses elaborated with goat milk, generating comparable results. To our knowledge, this is the first time that MHS-SPME has been applied to volatiles in cheeses. PMID:25127582

Rincón, Arturo A; Pino, Verónica; Ayala, Juan H; Afonso, Ana M




SciTech Connect

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.

Aihua Zhang; Qisheng Ma; William A. Goddard; Yongchun Tang



Increased Selectivity in the Formation of the Phenoxy Ether of Methyl Lesquerolate over Chloroalkyl-modified SBA-15-SO3H Catalysts  

Technology Transfer Automated Retrieval System (TEKTRAN)

A novel synthetic catalysis was developed for selective modification of useful bioproducts from the oil of Lesquerella fendlerii, an agricultural commodity of increasing importance. Modification of the surface of the solid acid catalyst SBA-15-SO3H with the chloroalkyl groups CH2CH2Cl has improved ...


Spectroscopic studies of solid-state forms of donepezil free base and salt forms with various salicylic acids  

NASA Astrophysics Data System (ADS)

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.

Brittain, Harry G.



Spectroscopic and XRD characterisation of zeolite catalysts active for the oxidative methylation of benzene with methane.  


The benzene methylation with methane over zeolite catalysts was previously shown in our laboratory to require the presence of oxygen. Thus, a two-step mechanism involving the intermediate formation of methanol by partial oxidation of methane followed by the methylation of benzene with methanol in the second step, was postulated. This paper now reports the results of the charac