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Sample records for adding formic acid

  1. Formic acid

    Integrated Risk Information System (IRIS)

    Formic acid ; CASRN 64 - 18 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  2. Formation of formic acid and organic peroxides in the ozonolysis of ethene with added water vapour

    NASA Astrophysics Data System (ADS)

    Horie, Osamu; Neeb, Peter; Limbach, Stefan; Moortgat, Geert K.

    1994-07-01

    Ozonolysis of C2H4 was carried out in a 580 l glass reaction vessel at 1-5 ppm reactant concentrations, with added water vapour. Under dry conditions ([H2O]0 = 0.5 ppm), HCHO, CO, CO2, (CHO)2O (formic acid anhydride), H2O2, and CH3OOH were identified as the reaction products. Under wet conditions ([H2O]0 = 2 × 104 ppm), HCOOH yields approaching ca. 20% of the converted C2H4, were observed, while no (CHO)2O was formed. Hydroxymethyl hydroperoxide, HOCH2OOH, was observed as the major peroxide, and found to be formed only in the presence of water vapour. Direct reactions of H2O vapour with the excited CH2OO* radicals and with stabilized CH2OO radicals are postulated to explain the formation of HCOOH and HOCH2OOH in the presence of water vapour, respectively.

  3. GLYCOLIC - FORMIC ACID FLOWSHEET DEVELOPMENT

    SciTech Connect

    Pickenheim, B.; Stone, M.; Newell, J.

    2010-11-08

    glycolic acid added. The outstanding issues regarding the glycolic/formic flowsheet include increasing understanding of the impact on glass REDOX control and increased metal solubility, particularly iron, during processing. Additionally, evaluations of the utility of the flowsheet over varying sludge compositions should be completed to ensure flowsheet robustness. Work has already been initiated to further understand the REDOX and iron solubility areas.

  4. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. The food additive, formic acid, may be safely used in accordance with the...) The top foot of silage stored should not contain formic acid and (2) Silage should not be fed...

  5. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. The food additive, formic acid, may be safely used in accordance with the...) The top foot of silage stored should not contain formic acid and (2) Silage should not be fed...

  6. Dehydrogenation of Formic Acid by Heterogeneous Catalysts.

    PubMed

    Li, Jun; Zhu, Qi-Long; Xu, Qiang

    2015-01-01

    Formic acid has recently been considered as one of the most promising hydrogen storage materials. The basic concept is briefly discussed and the research progress is detailledly reviewed on the dehydrogenation of aqueous formic acid by heterogeneous catalysts. PMID:26507481

  7. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. Formic acid may be safely used as a preservative in hay crop silage in an.... The top foot of silage stored should not contain formic acid and silage should not be fed to...

  8. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  9. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Formic acid. 186.1316 Section 186.1316 Food and....1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and is contained in the free...

  10. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  11. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  12. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  13. The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

    NASA Astrophysics Data System (ADS)

    Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

    2014-04-01

    Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

  14. Desulfurization of coal using formic acid

    SciTech Connect

    Wang, G.; Perkson, A.; Trass, O.

    1995-12-31

    Desulfurization of preoxidized Illinois Basin coal, IBC-108, with formic acid has been studied using a factorial design with four process variables: temperature, reaction time, amount of formic acid and amount of hydrogen peroxide used in the preoxidation step. Maximum total removal of 74% sulfur was achieved by pre-treatment of 5 g coal with 10 ml hydrogen peroxide followed by reaction with 7.5 ml formic acid at 500 C, in a 300 ml batch reactor. The results show that oxidation with hydrogen peroxide significantly enhances the level of desulfurization that may be obtained with subsequent chemical or thermal treatments.

  15. Elastic electron scattering from formic acid

    SciTech Connect

    Trevisan, Cynthia S.; Orel, Ann E.; Rescigno, Thomas N.

    2006-07-31

    Following our earlier study on the dynamics of low energy electron attachment to formic acid, we report the results of elastic low-energy electron collisions with formic acid. Momentum transfer and angular differential cross sections were obtained by performing fixed-nuclei calculations employing the complex Kohn variational method. We make a brief description of the technique used to account for the polar nature of this polyatomic target and compare our results with available experimental data.

  16. Atmospheric measurements of pyruvic and formic acid

    NASA Technical Reports Server (NTRS)

    Andreae, Meinrat O.; Li, Shao-Meng; Talbot, Robert W.

    1987-01-01

    Pyruvic acid, a product of the atmospheric oxidation of cresols and probably of isoprene, has been determined together with formic acid in atmospheric aerosols and rain as well as in the vapor phase. Both acids are present predominantly as vapor; only about 10-20 percent of the total atmospheric pyruvate and 1-2 percent of the total formate are in the particulate phase. The concentrations of pyruvic and formic acid are highly correlated, with typical formic-to-pyruvic ratios of 10-30 in the gas phase, 20-30 in rain, and 2-10 in aerosols. The gas-phase and rain ratios are comparable to those predicted to result from isoprene oxidation. Pyruvic acid levels were similar in the eastern United States (during summer) and the Amazon Basin, suggesting that natural processes, particularly the photochemical oxidation of isoprene, could account for most of the pyruvic acid present in the atmosphere.

  17. Photolysis of formic acid at 355 nm

    NASA Astrophysics Data System (ADS)

    Martinez, Denhi; Bautista, Teonanacatl; Guerrero, Alfonso; Alvarez, Ignacio; Cisneros, Carmen

    2015-05-01

    Formic acid is well known as a food additive and recently an application on fuel cell technology has emerged. In this work we have studied the dissociative ionization process by multiphoton absorption of formic acid molecules at 355nm wavelength photons, using TOF spectrometry in reflectron mode (R-TOF). Some of the most abundant ionic fragments produced are studied at different settings of the laser harmonic generator. The dependence of the products on these conditions is reported. This work was supported by CONACYT Project 165410 and PAPIIT IN102613 and IN101215.

  18. Formic acid fuel cells and catalysts

    SciTech Connect

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

    2010-06-22

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

  19. Tested Demonstrations: Color Oscillations in the Formic Acid-Nitric Acid-Sulfuric Acid System.

    ERIC Educational Resources Information Center

    Raw, C. J. G.; And Others

    1983-01-01

    Presented are procedures for demonstrating the production of color oscillations when nitric acid is added to a formic acid/concentrated sulfuric acid mixture. Because of safety considerations, "Super-8" home movie of the color changes was found to be satisfactory for demonstration purposes. (JN)

  20. GLYCOLIC-FORMIC ACID FLOWSHEET FINAL REPORT FOR DOWNSELECTION DECISION

    SciTech Connect

    Lambert, D.; Pickenheim, B.; Stone, M.; Newell, J.; Best, D.

    2011-03-10

    total solids content and may be effective at acid stoichiometries below 100%, although no testing was performed below 100% acid stoichiometry. There are several issues related to the development of the glycolic-formic flowsheet. First, the measurement of anions using the new glycolate anion procedure likely needs to be optimized to improve the accuracy of the anions important to DWPF processing and REDOX prediction. Second, the existing REDOX equation with an added term for glycolate did not accurately predict the glass REDOX for the glycolic-formic flowsheet. Improvement of the anion measurement or modification of the REDOX methodology or equation may be necessary to improve the REDOX prediction. Last, the glycolic-formic flowsheet dissolves a number of metals, including iron. This leads to a thinner slurries but also dissolves up a portion of the iron, which is currently used for criticality control. It is recommended that DWPF continue to support development of the glycolic-formic flowsheet. This flowsheet meets or outperforms the baseline flowsheet in off-gas generation, mercury removal, product rheology and general ease of processing. Additional testing is in progress to demonstrate the effectiveness of the nitric-glycolic-formic flowsheet in processing a wide sludge processing window using the matrix sludge simulants.

  1. Polymerization of Formic Acid under High Pressure

    SciTech Connect

    Goncharov, A F; Manaa, M R; Zaug, J M; Fried, L E; Montgomery, W B

    2004-08-23

    We report combined Raman, infrared (IR) and x-ray diffraction (XRD) measurements, along with ab initio calculations on formic acid under pressure up to 50 GPa. Contrary to the report of Allan and Clark (PRL 82, 3464 (1999)), we find an infinite chain low-temperature Pna2{sub 1} structure consisting of trans molecules to be a high-pressure phase at room temperature. Our data indicate the symmetrization and a partially covalent character of the intra-chain hydrogen bonds above approximately 20 GPa. Raman spectra and XRD patterns indicate a loss of the long-range order at pressures above 40 GPa with a large hysteresis at decompression. We attribute this behavior to a three-dimensional polymerization of formic acid.

  2. Crossover of formic acid through Nafion ® membranes

    NASA Astrophysics Data System (ADS)

    Rhee, Young-Woo; Ha, Su Y.; Masel, Richard I.

    Formic acid has been proposed as a possible fuel for miniature fuel cells, because formic acid is expected to show low crossover and easy water management. In this paper, the permeation of formic acid through Nafion ® membranes is investigated at room temperature. It is found that the permeation of formic acid through Nafion ® 112 and 117 is much lower than that of methanol. For example, at a 1 M concentration, the steady state flux of formic acid through Nafion ® 117 is only 2.03±0.07×10 -8 mol/cm 2 s. By comparison, previous workers have observed a methanol flux of 3 to 6×10 -6 mol/cm 2 s through Nafion ® 117 under similar conditions. The flux through Nafion ® 117 increases with increasing formic acid concentration, reaching a maximum of 1.86±0.11×10 -7 mol/cm 2 s at a formic acid concentration of 10 M. The flux of formic acid is about a factor of two higher through Nafion ® 112 than through Nafion ® 117 but still low. These results show that the permeation of formic acid through Nafion ® is much slower than the permeation of methanol through the same membrane. Consequently, formic acid is an attractive alternative fuel for small polymer electrolyte membrane (PEM) fuel cells.

  3. Nitric acid-formic acid compatibility in DWPF

    SciTech Connect

    Eibling, R.E.

    1992-10-20

    The addition of the Nitric Acid Flowsheet to the DWPF feed preparation process introduces nitric acid into a vessel which will subsequently receive a formic acid solution. The combination of these two acids suggests that a denitration reaction might occur. This memorandum reviews the conditions under which a denitration reaction is possible and compares these conditions to DWPF operating conditions.

  4. Polymerization of formic acid under high pressure

    SciTech Connect

    Goncharov, A.F.; Manaa, M.R.; Zaug, J.M.; Gee, R.H.; Fried, L.E.; Montgomery, W.B.

    2010-07-19

    We report Raman, infrared, and x-ray diffraction (XRD) measurements, along with ab initio calculations on formic acid (FA) under pressure up to 50 GPa. We find an infinite chain Pna2{sub 1} structure to be a high-pressure phase at room temperature. Our data indicate the symmetrization and a partially covalent character of the intrachain hydrogen bonds above approximately 20 GPa. Raman spectra and XRD patterns indicate a loss of long-range order at pressures above 40 GPa, with a large hysteresis upon decompression. We attribute this behavior to a three-dimensional polymerization of FA.

  5. Repellent Effect of Formic Acid Against the Red Imported Fire Ant (Hymenoptera: Formicidae): A Field Study.

    PubMed

    Wang, Cai; Henderson, Gregg

    2016-04-01

    Previous studies showed that the formic acid secreted by tawny crazy ants not only has fumigation toxicity to the red imported fire ant, Solenopsis invicta Buren (Chen et al. 2013), but also can detoxify fire ant venom (LeBrun et al. 2014). These lead us to a field study to determine if low concentrations of formic acid might be useful in repelling S. invicta. Filter paper discs treated with 1.3% or 5% formic acid (v: v) or distilled water (control) were placed on each of the 46 S. invicta mounds and a disturbance was created. For a minute or less, there were significantly more defending ants on the control discs than that on the paper discs treated with formic acid. After food was added and for the next 40 min, there were significantly more foraging ants on the control discs compared to the treated discs. At 50 min into the test, the number of foraging ants on the control and 1.3% formic acid-treated discs was similar, but both were significantly higher than that on the 5% formic acid-treated discs. In addition, the active foraging (≥10 ants stayed on or around the food) and burying behavior (soil particles were deposited around the food) continued to be inhibited by 5% formic acid. The potential application and ecological significant of this repellent effect is discussed. PMID:26700488

  6. Suicidal chemistry: combined intoxication with carbon monoxide and formic acid.

    PubMed

    Bakovic, Marija; Nestic, Marina; Mayer, Davor

    2016-05-01

    Herein, we present a rare case of suicidal intoxication with carbon monoxide produced via reaction of formic and sulphuric acid with additional toxic effect of formic acid. The deceased was a 22-year-old men found dead in the bathroom locked from the inside. A bucket filled with liquid was found next to him, together with an almost empty canister labeled "formic acid" and another empty unlabeled canister. The postmortem examination revealed corrosive burns of the face, neck and chest, cherry-pink livor mortis, corrosive injury to the oropharyngeal area and trachea, subpleural petechiae, 100 mL of blood in stomach and superficial erosions of stomach mucosa. Toxicology analysis revealed 30% of carboxyhemoglobin in the femoral blood and the presence of the formic acid in various samples. Quantitative analysis of formic acid was performed by measuring methyl ester derivative of formic acid by using headspace gas chromatography with flame ionization detection. The highest concentration of formic acid was measured in the lungs (0.55 g/kg), gastric content (0.39 g/L), and blood (0.28 g/L). In addition, it was established that content of the unlabeled canister had a pH value of 0.79 and contained sulphuric ions. Morphological and toxicology findings suggested that the main route of exposure to formic acid was inhalation of vapors with a possible ingestion of only small amount of liquid acid. The cause of death was determined to be combined intoxication with carbon monoxide and formic acid. PMID:26041513

  7. A prolific catalyst for dehydrogenation of neat formic acid.

    PubMed

    Celaje, Jeff Joseph A; Lu, Zhiyao; Kedzie, Elyse A; Terrile, Nicholas J; Lo, Jonathan N; Williams, Travis J

    2016-01-01

    Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

  8. A prolific catalyst for dehydrogenation of neat formic acid

    PubMed Central

    Celaje, Jeff Joseph A.; Lu, Zhiyao; Kedzie, Elyse A.; Terrile, Nicholas J.; Lo, Jonathan N.; Williams, Travis J.

    2016-01-01

    Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

  9. Water and formic acid aggregates: a molecular dynamics study.

    PubMed

    Vardanega, Delphine; Picaud, Sylvain

    2014-09-14

    Water adsorption around a formic acid aggregate has been studied by means of molecular dynamics simulations in a large temperature range including tropospheric conditions. Systems of different water contents have been considered and a large number of simulations has allowed us to determine the behavior of the corresponding binary formic acid-water systems as a function of temperature and humidity. The results clearly evidence a threshold temperature below which the system consists of water molecules adsorbed on a large formic acid grain. Above this temperature, formation of liquid-like mixed aggregates is obtained. This threshold temperature depends on the water content and may influence the ability of formic acid grains to act as cloud condensation nuclei in the Troposphere. PMID:25217941

  10. The effect of formic acid concentration on the conductivity and corrosion resistance of chromium carbide coatings electroplated with trivalent chromium

    NASA Astrophysics Data System (ADS)

    Lu, Chen-En; Pu, Nen-Wen; Hou, Kung-Hsu; Tseng, Chun-Chieh; Ger, Ming-Der

    2013-10-01

    Different concentrations of formic acid were added into a trivalent chromium electroplating solution to produce chromium carbide (Crsbnd C) coatings. The influence of the formic acid concentration on chemical composition, microstructure, surface morphology, corrosion resistance, conductivity and carbon content of the resulting Crsbnd C coatings was studied. Formic acid was found to increase the carbon content in the coatings so as to form Crsbnd C films. These coatings had a nearly amorphous structure containing Cr, Cr2O3, and various Crsbnd C compounds with carbon content uniformly distributed throughout the coatings. The carbon content and the conductivity of the Crsbnd C layer were correlated with formic acid concentration. For a formic acid concentration of 2 M, the Crsbnd C layer had the highest carbon content (∼28%), the lowest contact resistance, and the best corrosion resistance along with a corrosion current density of ∼6.4 × 10-7 A/cm2.

  11. Aqueous-phase source of formic acid in clouds

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.; Davis, D. D.

    1983-01-01

    The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

  12. Reductive Leaching of Low-Grade Pyrolusite with Formic Acid

    NASA Astrophysics Data System (ADS)

    Lu, Youzhi; Ma, Huaju; Huang, Runjun; Yuan, Aiqun; Huang, Zengwei; Zhou, Zeguang

    2015-08-01

    The extraction of manganese from low-grade pyrolusite is investigated using formic acid as reductant in sulfuric acid medium. The effects of volumes of formic acid, concentration of sulfuric acid, liquid to solid ratio (L/S), leaching time, and temperature on leaching efficiency of manganese, iron, and aluminum are valuated with single-factor experiments. The results show that the leaching efficiency of manganese reached 90.08 pct with 80.70 pct of iron and 31.55 pct of aluminum under the optical conditions: 15 pct H2SO4(v/v) 60 ml, 4 ml formic acid, and 2 hours leaching time at 363 K (90 °C).

  13. Evaluation of formic acid and propionic acid feed additives on environmental and cecal Salmonella Typhimurium in broilers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Three trials were performed to evaluate the effectiveness of formic acid and propionic acid on environmental and cecal recovery of Salmonella. Trial 1: Chicks (33/pen) were placed in one of 3 treatments with 8 reps, Trt A: 1 kg/ton formic acid, Trt B: 5 kg/ton formic acid, and Trt C: no formic acid....

  14. Low contaminant formic acid fuel for direct liquid fuel cell

    DOEpatents

    Masel, Richard I.; Zhu, Yimin; Kahn, Zakia; Man, Malcolm

    2009-11-17

    A low contaminant formic acid fuel is especially suited toward use in a direct organic liquid fuel cell. A fuel of the invention provides high power output that is maintained for a substantial time and the fuel is substantially non-flammable. Specific contaminants and contaminant levels have been identified as being deleterious to the performance of a formic acid fuel in a fuel cell, and embodiments of the invention provide low contaminant fuels that have improved performance compared to known commercial bulk grade and commercial purified grade formic acid fuels. Preferred embodiment fuels (and fuel cells containing such fuels) including low levels of a combination of key contaminants, including acetic acid, methyl formate, and methanol.

  15. Hydrogen Storage in the Carbon Dioxide - Formic Acid Cycle.

    PubMed

    Fink, Cornel; Montandon-Clerc, Mickael; Laurenczy, Gabor

    2015-01-01

    This year Mankind will release about 39 Gt carbon dioxide into the earth's atmosphere, where it acts as a greenhouse gas. The chemical transformation of carbon dioxide into useful products becomes increasingly important, as the CO(2) concentration in the atmosphere has reached 400 ppm. One approach to contribute to the decrease of this hazardous emission is to recycle CO(2), for example reducing it to formic acid. The hydrogenation of CO(2) can be achieved with a series of catalysts under basic and acidic conditions, in wide variety of solvents. To realize a hydrogen-based charge-discharge device ('hydrogen battery'), one also needs efficient catalysts for the reverse reaction, the dehydrogenation of formic acid. Despite of the fact that the overwhelming majority of these reactions are carried out using precious metals-based catalysts (mainly Ru), we review here developments for catalytic hydrogen evolution from formic acid with iron-based complexes. PMID:26842324

  16. [Parenteral administration of formic acid in alternative medicine].

    PubMed

    Helmstädter, A

    2001-01-01

    Treatment of rheumatic and other diseases through immersion in an anthill is reported in German folk medicine. In the first half of the twentieth century, the physicians Eduard and Egon Krull (1842-1914 and 1879-1936, respectively) as well as Albrecht Reuter (1863-1937) recommended injections of diluted formic acid to treat tuberculosis, gout, arthritis, renal disorders and other complaints. Between 1930 and 1960, more than 15 different commercial preparations were marketed, and Egon Krull invented a drug series called "Myrmekan". Formic acid inhalations were recommended by Sigmund von Kapff (1864-1946) at a time when the acid was rarely used in homeopathy. In the 1950s, the injection of formic acid was regarded as one of the most important procedures in alternative medicine. PMID:12360988

  17. State-selected imaging studies of formic acid photodissociation dynamics

    SciTech Connect

    Huang Cunshun; Yang Xueming; Zhang Cuimei

    2010-04-21

    The photodissociation dynamics of formic acid have been studied using the velocity map ion imaging at the UV region. The measurements were made with resonance enhancement multiphoton ionization (REMPI) spectroscopy and dc slicing ion imaging. The OH REMPI spectrum from the photodissociation of formic acid at 244 nm has been recorded. The spectrum shows low rotational excitation (N{<=}4). By fixing the probe laser at the specific rotational transitions, the resulting OH images from various dissociation wavelengths have been accumulated. The translational energy distributions derived from the OH images imply that about half of the available energies go to the photofragments internal excitation. The dissociation dynamics of formic acid were also discussed in view of the recent theoretical calculations.

  18. Enhanced formic acid oxidation on Cu-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Dai, Lin; Zou, Shouzhong

    Developing catalysts with high activity and high resistance to surface poisoning remains a challenge in direct formic acid fuel cell research. In this work, copper-palladium nanoparticles were formed through a galvanic replacement process. After electrochemically selective dissolution of surface Cu, Pd-enriched Cu-Pd nanoparticles were formed. These particles exhibit much higher formic acid oxidation activities than that on pure Pd nanoparticles, and they are much more resistant to the surface poisoning. Possible mechanisms of catalytic activity enhancement are briefly discussed.

  19. CO2 Hydrogenation to Formic Acid on Ni(110)

    SciTech Connect

    Peng, Guowen; Sibener, S. J.; Schatz, George C.; Mavrikakis, Manos

    2012-03-06

    Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO2) on Ni(110). The energetics of surface and subsurface H reacting with surface CO2 to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO2 can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid.We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO2 hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO2. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.

  20. Toxicity of formic acid against red imported fire ants, Solenopsis invicta Buren

    Technology Transfer Automated Retrieval System (TEKTRAN)

    BACKGROUND: Formic acid is a common defensive chemical of formicine ants. Ants often compete with other ants for resources. However, the toxicity of formic acid to any ant species has not been well understood. This study examined the toxicity of formic acid against the red imported fire ants, Sole...

  1. TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORN)

    Atmospheric Science Data Center

    2015-02-04

    TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORN) News:  TES News Join ... L2 Platform:  TES/Aura L2 Formic Acid Spatial Coverage:  5.3 x 8.5 km nadir Spatial ... Access:  OPeNDAP Parameters:  Formic Acid Volume Mixing Ratio Precision Vertical Resolution Order ...

  2. TES/Aura L2 Formic Acid (FOR) Lite Nadir (TL2FORLN)

    Atmospheric Science Data Center

    2015-06-16

    TES/Aura L2 Formic Acid (FOR) Lite Nadir (TL2FORLN) News:  TES News ... L2 Instrument:  TES/Aura L2 Formic Acid Spatial Coverage:  5.3 km nadir Spatial ... Access:  OPeNDAP Parameters:  Formic Acid Volume Mixing Ratio Vertical Resolution Precision Order ...

  3. TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORNS)

    Atmospheric Science Data Center

    2015-02-04

    TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORNS) News:  TES News Join ... L2 Platform:  TES/Aura L2 Formic Acid Spatial Coverage:  5.3 x 8.5 km nadir Spatial ... Access:  OPeNDAP Parameters:  Formic Acid Volume Mixing Ratio Precision Vertical Resolution Order ...

  4. GLYCOLIC-FORMIC ACID FLOWSHEET SLUDGE MATRIX STUDY

    SciTech Connect

    Lambert, D.; Koopman, D.

    2011-06-30

    Testing was completed to demonstrate the viability of the newly developed glycolic acid/formic acid flowsheet on processing in the Defense Waste Processing Facility's (DWPF) Chemical Process Cell (CPC). The Savannah River National Laboratory (SRNL) initiated a sludge matrix study to evaluate the impact of changing insoluble solid composition on the processing characteristics of slurries in DWPF. Four sludge simulants were prepared to cover two compositional ranges in the waste. The first was high iron/low aluminum versus low iron/high aluminum (referred to as HiFe or LoFe in this report). The second was high calcium-manganese/low nickel, chromium, and magnesium versus low calcium-manganese/high nickel, chromium, and magnesium (referred to as HiMn or LoMn in this report). These two options can be combined to form four distinct sludge compositions. The sludge matrix study called for testing each of these four simulants near the minimum acid required for nitrite destruction (100% acid stoichiometry) and at a second acid level that produced significant hydrogen by noble metal catalyzed decomposition of formic acid (150% acid stoichiometry). Four simulants were prepared based on the four possible combinations of the Al/Fe and Mn-Ca/Mg-Ni-Cr options. Preliminary simulant preparation work has already been documented. The four simulants were used for high and low acid testing. Eight planned experiments (GF26 to GF33) were completed to demonstrate the viability of the glycolic-formic flowsheet. Composition and physical property measurements were made on the SRAT product. Composition measurements were made on the condensate from the Mercury Water Wash Tank (MWWT), Formic Acid Vent Condenser (FAVC), ammonia scrubber and on SRAT samples pulled throughout the SRAT cycle. Updated values for formate loss and nitrite-tonitrate conversion were found that can be used in the acid calculations for future sludge matrix process simulations with the glycolic acid/formic acid flowsheet

  5. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... assure safe use of the additive, in addition to the other information required by the Federal Food, Drug... acid. (4) To assure safe use of the additive, in addition to the other information required by...

  6. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... assure safe use of the additive, in addition to the other information required by the Federal Food, Drug... acid. (4) To assure safe use of the additive, in addition to the other information required by...

  7. Onboard Catalysis of Formic Acid for Hydrogen Fueled Vehicles

    NASA Astrophysics Data System (ADS)

    Karim, Altaf; Mamoor, Muhammad

    2015-03-01

    Metal hydrides are used as a medium of hydrogen storage in hydrogen powered vehicles. Such hydride materials cannot store hydrogen more than 10 wt%. The bottleneck in this issue is the reversible storage of hydrogen at ambient temperature and pressure. Alternatively formic acid is becoming more popular medium for the onboard hydrogen production for these vehicles. Its decomposition on metal surfaces and nanostructures is considered to be a potential method to produce CO-free hydrogen at near ambient temperatures. We applied Density Functional Theory (DFT) based Kinetic Monte Carlo (KMC) simulations as our tool to study the reaction kinetics of hydrogen production from formic acid on different catalytic surfaces and nano structures (Au, Pd, Rh, Pt). Our results show that nanostructures and artificially engineered bimetallic catalysts give higher rate of hydrogen production then their monometallic counter parts under various temperature and pressure conditions.

  8. Kinetic and stoichiometric characterization of organoautotrophic growth of Ralstonia eutropha on formic acid in fed-batch and continuous cultures

    PubMed Central

    Grunwald, Stephan; Mottet, Alexis; Grousseau, Estelle; Plassmeier, Jens K; Popović, Milan K; Uribelarrea, Jean-Louis; Gorret, Nathalie; Guillouet, Stéphane E; Sinskey, Anthony

    2015-01-01

    Formic acid, acting as both carbon and energy source, is a safe alternative to a carbon dioxide, hydrogen and dioxygen mix for studying the conversion of carbon through the Calvin–Benson–Bassham (CBB) cycle into value-added chemical compounds by non-photosynthetic microorganisms. In this work, organoautotrophic growth of Ralstonia eutropha on formic acid was studied using an approach combining stoichiometric modeling and controlled cultures in bioreactors. A strain deleted of its polyhydroxyalkanoate production pathway was used in order to carry out a physiological characterization. The maximal growth yield was determined at 0.16 Cmole Cmole−1 in a formate-limited continuous culture. The measured yield corresponded to 76% to 85% of the theoretical yield (later confirmed in pH-controlled fed-batch cultures). The stoichiometric study highlighted the imbalance between carbon and energy provided by formic acid and explained the low growth yields measured. Fed-batch cultures were also used to determine the maximum specific growth rate (μmax = 0.18 h−1) and to study the impact of increasing formic acid concentrations on growth yields. High formic acid sensitivity was found in R eutropha since a linear decrease in the biomass yield with increasing residual formic acid concentrations was observed between 0 and 1.5 g l−1. PMID:25123319

  9. Low-energy electron scattering by formic acid

    SciTech Connect

    Trevisan, C. S.; Orel, A. E.; Rescigno, T. N.

    2006-10-15

    We report the results of fixed-nuclei complex Kohn variational calculations of elastic electron scattering by formic acid, HCOOH. Momentum transfer and angular differential cross sections for incident electron energies ranging from 0.1 to 15 eV are presented and compared to available experimental data. The low-energy behavior of the cross section is analyzed and found to be consistent with the existence of a virtual state.

  10. Hydrogen production by photoelectrochemically splitting solutions of formic acid.

    PubMed

    Li, Lei; Guo, Wenliang; Zhu, Yusong; Wu, Yuping

    2011-10-17

    A TiO₂/FTO (FTO=fluorine-doped tin oxide) electrode was prepared by dip-coating FTO in a suspension of TiO₂ prepared from a sol-gel method and was used as a photoanode to split an aqueous solution of formic acid to produce hydrogen. The surface of the TiO₂/FTO film was covered with assemblies of TiO₂ nanoparticles with a diameter of approximately 20 nm. Under irradiation by using a Xe lamp, splitting of formic acid was performed at different applied current densities. Compared to splitting water or utilizing FTO and Pt foil as the anode, the splitting voltage is much lower and can be as low as -0.27 V. The results show that the splitting voltage is related to the concentration of free formate groups. The evolution rate of hydrogen measured by using gas chromatography is 130 μmol h⁻¹ at a current density of 20 mA cm⁻² and the energy-conversion efficiency can be 1.79 %. Photoelectrolysis of formic acid has the potential to be an efficient way to produce hydrogen with a high energy-conversion efficiency. PMID:21994155

  11. Carbon nanofiber supported bimetallic PdAu nanoparticles for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Qin, Yuan-Hang; Jiang, Yue; Niu, Dong-Fang; Zhang, Xin-Sheng; Zhou, Xing-Gui; Niu, Li; Yuan, Wei-Kang

    2012-10-01

    Carbon nanofiber (CNF) supported PdAu nanoparticles are synthesized with sodium citrate as the stabilizing agent and sodium borohydride as the reducing agent. High resolution transmission electron microscopy (HRTEM) characterization indicates that the synthesized PdAu particles are well dispersed on the CNF surface and X-ray diffraction (XRD) characterization indicates that the alloying degree of the synthesized PdAu nanoparticles can be improved by adding tetrahydrofuran to the synthesis solution. The results of electrochemical characterization indicate that the addition of Au can promote the electrocatalytic activity of Pd/C catalyst for formic acid oxidation and the CNF supported high-alloying PdAu catalyst possesses better electrocatalytic activity and stability for formic acid oxidation than either the CNF supported low-alloying PdAu catalyst or the CNF supported Pd catalyst.

  12. Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone.

    PubMed

    van der Linde, Christian; Tang, Wai-Kit; Siu, Chi-Kit; Beyer, Martin K

    2016-08-26

    Gas-phase reactions of CO3 (.-) with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2 , which in turn transfer the electron to O3 . O3 (.-) reacts with CO2 to form CO3 (.-) . The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons. PMID:27400953

  13. Formic acid triggers the "Acid Crash" of acetone-butanol-ethanol fermentation by Clostridium acetobutylicum.

    PubMed

    Wang, Shaohua; Zhang, Yanping; Dong, Hongjun; Mao, Shaoming; Zhu, Yan; Wang, Runjiang; Luan, Guodong; Li, Yin

    2011-03-01

    Solvent production by Clostridium acetobutylicum collapses when cells are grown in pH-uncontrolled glucose medium, the so-called "acid crash" phenomenon. It is generally accepted that the fast accumulation of acetic acid and butyric acid triggers the acid crash. We found that addition of 1 mM formic acid into corn mash medium could trigger acid crash, suggesting that formic acid might be related to acid crash. When it was grown in pH-uncontrolled glucose medium or glucose-rich medium, C. acetobutylicum DSM 1731 containing the empty plasmid pIMP1 failed to produce solvents and was found to accumulate 0.5 to 1.24 mM formic acid intracellularly. In contrast, recombinant strain DSM 1731 with formate dehydrogenase activity did not accumulate formic acid intracellularly and could produce solvent as usual. We therefore conclude that the accumulation of formic acid, rather than acetic acid and butyric acid, is responsible for the acid crash of acetone-butanol-ethanol fermentation. PMID:21216898

  14. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media

    PubMed Central

    Moret, Séverine; Dyson, Paul J.; Laurenczy, Gábor

    2014-01-01

    The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M formic acid. In both solvents the catalysts can be reused multiple times without a decrease in activity. Worldwide demand for formic acid continues to grow, especially in the context of a renewable energy hydrogen carrier, and its production from CO2 without base, via the direct catalytic carbon dioxide hydrogenation, is considerably more sustainable than the existing routes. PMID:24886955

  15. Catalytic air oxidation of biomass-derived carbohydrates to formic acid.

    PubMed

    Li, Jiang; Ding, Dao-Jun; Deng, Li; Guo, Qing-Xiang; Fu, Yao

    2012-07-01

    An efficient catalytic system for biomass oxidation to form formic acid was developed. The conversion of glucose to formic acid can reach up to 52% yield within 3 h when catalyzed by 5 mol% of H(5)PV(2)Mo(10)O(40) at only 373 K using air as the oxidant. Furthermore, the heteropolyacid can be used as a bifunctional catalyst in the conversion of cellulose to formic acid (yield=35%) with air as the oxidant. PMID:22499553

  16. New Theoretical Insight into the Interactions and Properties of Formic Acid: Development of a Quantum-Based Pair Potential for Formic Acid.

    SciTech Connect

    Roszak, S; Gee, R; Balasubramanian, K; Fried, L

    2005-08-08

    We performed ab initio quantum chemical studies for the development of intra and intermolecular interaction potentials for formic acid for use in molecular dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter-molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment.

  17. New theoretical insight into the interactions and properties of formic acid: development of a quantum-based pair potential for formic acid.

    PubMed

    Roszak, Szczepan; Gee, Richard H; Balasubramanian, Krishnan; Fried, Laurence E

    2005-10-01

    We performed ab initio quantum-chemical studies for the development of intra- and intermolecular interaction potentials for formic acid for use in molecular-dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen-bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular-dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular-dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment. PMID:16238411

  18. Direct formic acid microfluidic fuel cell design and performance evolution

    NASA Astrophysics Data System (ADS)

    Moreno-Zuria, A.; Dector, A.; Cuevas-Muñiz, F. M.; Esquivel, J. P.; Sabaté, N.; Ledesma-García, J.; Arriaga, L. G.; Chávez-Ramírez, A. U.

    2014-12-01

    This work reports the evolution of design, fabrication and testing of direct formic acid microfluidic fuel cells (DFAμFFC), the architecture and channel dimensions are miniaturized from a thousand to few cents of micrometers. Three generations of DFAμFFCs are presented, from the initial Y-shape configuration made by a hot pressing technique; evolving into a novel miniaturized fuel cell based on microfabrication technology using SU-8 photoresist as core material; to the last air-breathing μFFC with enhanced performance and built with low cost materials and processes. The three devices were evaluated in acidic media in the presence of formic acid as fuel and oxygen/air as oxidant. Commercial Pt/C (30 wt. % E-TEK) and Pd/C XC-72 (20 wt. %, E-TEK) were used as cathode and anode electrodes respectively. The air-breathing μFFC generation, delivered up to 27.3 mW cm-2 for at least 30 min, which is a competitive power density value at the lowest fuel flow of 200 μL min-1 reported to date.

  19. Catalytic Conversion of Biomass for the Production of Hydrogen; Decomposition of Formic Acid

    NASA Astrophysics Data System (ADS)

    Azadi Manzour, Faraz

    Highly active bimetallic catalysts were synthesized and used for the decomposition of formic acid for the production of hydrogen. Ruthenium alloys were prepared and resulted in a maximum formic acid conversion of 68% (after one hour at 180 °C) and a turnover frequency of 0.7/s (at 5 wt% formic acid). The most promising catalysts were characterized by the means of X-ray diffraction and scanning electron microscopy. Kinetic studies were also carried out over these catalysts for the determination of reaction rate and turnover frequency. Promotion of Ru/C with tin, barium and cesium increased the formic acid conversion by 55%, 18% and 11% respectively.

  20. Addition of formic acid or starter cultures to liquid feed. Effect on pH, microflora composition, organic acid concentration and ammonia concentration.

    PubMed

    Canibe, N; Miquel, N; Miettinen, H; Jensen, B B

    2001-01-01

    Some of the charateristics of good quality fermented liquid feed (FLF) are low pH, high numbers of lactic acid bacteria, and low numbers of enterobacteria. In order to test strategies to avoid a proliferation of enterobacteria during the initial phase of FLF elaboration, two in vitro studies were carried out. Addition of various doses of formic acid or two different starter cultures were tested. Adding 0.1% formic acid or L. plantarum VTT E-78076 to the liquid feed seemed to be addecuate ways of inhibiting the growth of enterobacteria, without depleting the growth of lactic acid bacteria. PMID:15954629

  1. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation

    SciTech Connect

    Landon, L.F.

    1991-01-01

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO[sub 3] and NaNO[sub 2] with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  2. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation. Revision 1

    SciTech Connect

    Landon, L.F.

    1991-12-31

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO{sub 3} and NaNO{sub 2} with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  3. Photolysis and Radiolysis of Formic Acid: Relevances to Astrophysical Ices.

    NASA Astrophysics Data System (ADS)

    Andrade, D.; Domaracka, A.; da Silveira, E. F.; Rothard, H.; Boduc, P.

    2011-05-01

    Formic acid (HCOOH), has been observed in several astronomical sources such as comets, protostellar ices, dark molecular clouds, and regions associated with stellar formation. In some massive star-forming regions such as Orion KL and W51, HCOOH have been observed. In these regions, the presence of X-ray fields illuminating large portions could trigger the formation of photodissociation regions. Inside dense molecular clouds, cosmic rays are the main source of ionization and dissociation, as they are capable of penetrating these regions and inducing the formation of new molecules. In this work we simulate the effects produced by the soft X-ray photon and cosmic rays on condensed formic acid. The sputtering yields, the destruction rate of HCOOH, and the rate of formation of new molecular species were determined from recorded spectra in situ by Fourier transform infrared spectroscopy. The figure 1a shows the virgin HCOOH spectrum (red) and the spectra of formic acid irradiated up to a final fluence of 1013 ions/cm^2 (blue). The evolution of the column density of the newly formed species from ice as a function of fluences is shown in Fig. 1b. The measured HCOOH sputtering yield was about 10^4 molecules/impact, while the HCOOH destruction cross-section was 1,1 10-13 cm^2. Among the formed species are CO, CO_2, H_2O. Their formation cross section are 5,4 10-14 cm^2, 6,1 10-14 cm^2 and 7,4 10-14 cm^2 respectively. Considering the estimated flux of heavy particles of solar wind and of heavy nuclei cosmic rays, we calculated the typical molecular half-lives of frozen molecules in astrophysical surfaces due the presence of heavy particles. At Earth orbit, t1/2 ~ 9,5 x 10^6 years and assuming that the fluxes of solar wind and energetic solar particles are inversely proportional to 1/r^2, this value can be determined as a function of distance up to the heliopause. In this case: t1/2 ~ 4,0 10^6 years. In addition, the photodesorption yields for positive and negative ions were

  4. Investigation of secondary formation of formic acid: urban environment vs. oil and gas producing region

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Veres, P. R.; Warneke, C.; Roberts, J. M.; Gilman, J. B.; Koss, A.; Edwards, P. M.; Graus, M.; Kuster, W. C.; Li, S.-M.; Wild, R. J.; Brown, S. S.; Dubé, W. P.; Lerner, B. M.; Williams, E. J.; Johnson, J. E.; Quinn, P. K.; Bates, T. S.; Lefer, B.; Hayes, P. L.; Jimenez, J. L.; Weber, R. J.; Zamora, R.; Ervens, B.; Millet, D. B.; Rappenglück, B.; de Gouw, J. A.

    2015-02-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site (Pasadena) in June-July 2010 during CalNex (California Research at the Nexus of Air Quality and Climate Change) and a site in an oil and gas producing region (Uintah Basin) in January-February 2013 during UBWOS 2013 (Uintah Basin Winter Ozone Studies) will be discussed. Although the VOC (volatile organic compounds) compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 99%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Compared to the original MCM model that includes only ozonolysis of unsaturated organic compounds and OH oxidation of acetylene, when we updated yields of ozonolysis of alkenes and included OH oxidation of isoprene, vinyl alcohol chemistry, reaction of formaldehyde with HO2, oxidation of aromatics, and reaction of CH3O2 with OH, the model predictions for formic acid were improved by a factor of 6.4 in UBWOS 2013 and 4.5 in CalNex, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 19 and 45% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be 0-6 and 0-5% in UBWOS 2013 and CalNex, respectively. We observe that

  5. Influence of Sodium Carbonate on Decomposition of Formic Acid by Discharge inside Bubble in Water

    NASA Astrophysics Data System (ADS)

    Iwabuchi, Masashi; Takahashi, Katsuyuki; Takaki, Koichi; Satta, Naoya

    2015-09-01

    An influence of sodium carbonate on decomposition of formic acid by discharge inside bubble in water was investigated. Oxygen or argon gases were injected into the water through a vertically positioned glass tube, in which the high-voltage wire electrode was placed to generate plasmas at low applied voltage. The concentration of formic acid was determined by ion chromatography. In the case of addition of sodium carbonate, the pH value increased with decomposition of the formic acid. In the case of oxygen injection, the increase of pH value contributed to improve an efficiency of the formic acid decomposition because the reaction rate of ozone and formic acid increased with increasing pH value. In the case of argon injection, the decomposition rate was not affected by the pH value owing to the high rate constants for loss of hydroxyl radicals.

  6. [Gas chromatographic determination of formic acid in urine as carbon monoxide (author's transl)].

    PubMed

    Angerer, J

    1976-02-01

    A gas chromatographic method for determining formic acid in human urine is described. The analytical reliability of this method fullfills the criteria of statistical quality control. The rate of recovery is 101.2 to 105.7% the variability coefficients lie between 2.9 and 7.2%. The selectivity of this method is demonstrated by analysing a group of components normally occuring in urine which did not interfere with the determination of formic acid. The detection limit of about 4.3 mumol/1 formic acid in urine permits the determination of the concentration of formic acid in the urine of normal persons. The concentrations of formic acid in the urine of a group of normal persons lies between 0 and 2.79 mmol/1. The average concentration was 0.39 +/- 0.60 mmol/1. PMID:1249528

  7. Efficient dehydrogenation of formic acid using an iron catalyst.

    PubMed

    Boddien, Albert; Mellmann, Dörthe; Gärtner, Felix; Jackstell, Ralf; Junge, Henrik; Dyson, Paul J; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2011-09-23

    Hydrogen is one of the essential reactants in the chemical industry, though its generation from renewable sources and storage in a safe and reversible manner remain challenging. Formic acid (HCO(2)H or FA) is a promising source and storage material in this respect. Here, we present a highly active iron catalyst system for the liberation of H(2) from FA. Applying 0.005 mole percent of Fe(BF(4))(2)·6H(2)O and tris[(2-diphenylphosphino)ethyl]phosphine [P(CH(2)CH(2)PPh(2))(3), PP(3)] to a solution of FA in environmentally benign propylene carbonate, with no further additives or base, affords turnover frequencies up to 9425 per hour and a turnover number of more than 92,000 at 80°C. We used in situ nuclear magnetic resonance spectroscopy, kinetic studies, and density functional theory calculations to explain possible reaction mechanisms. PMID:21940890

  8. LABORATORY STUDIES ON THE FORMATION OF FORMIC ACID (HCOOH) IN INTERSTELLAR AND COMETARY ICES

    SciTech Connect

    Bennett, Chris J.; Kim, Yong Seol; Kaiser, Ralf I.; Hama, Tetsuya; Kawasaki, Masahiro

    2011-01-20

    Mixtures of water (H{sub 2}O) and carbon monoxide (CO) ices were irradiated at 10 K with energetic electrons to simulate the energy transfer processes that occur in the track of galactic cosmic-ray particles penetrating interstellar ices. We identified formic acid (HCOOH) through new absorption bands in the infrared spectra at 1690 and 1224 cm{sup -1} (5.92 and 8.17 {mu}m, respectively). During the subsequent warm-up of the irradiated samples, formic acid is evident from the mass spectrometer signal at the mass-to-charge ratio, m/z = 46 (HCOOH{sup +}) as the ice sublimates. The detection of formic acid was confirmed using isotopically labeled water-d2 with carbon monoxide, leading to formic acid-d2 (DCOOD). The temporal fits of the reactants, reaction intermediates, and products elucidate two reaction pathways to formic acid in carbon monoxide-water ices. The reaction is induced by unimolecular decomposition of water forming atomic hydrogen (H) and the hydroxyl radical (OH). The dominating pathway to formic acid (HCOOH) was found to involve addition of suprathermal hydrogen atoms to carbon monoxide forming the formyl radical (HCO); the latter recombined with neighboring hydroxyl radicals to yield formic acid (HCOOH). To a lesser extent, hydroxyl radicals react with carbon monoxide to yield the hydroxyformyl radical (HOCO), which recombined with atomic hydrogen to produce formic acid. Similar processes are expected to produce formic acid within interstellar ices, cometary ices, and icy satellites, thus providing alternative processes for the generation of formic acid whose abundance in hot cores such as Sgr-B2 cannot be accounted for solely by gas-phase chemistry.

  9. Effect of formic acid formulations on honey bee (Hymenoptera: Apidae) colonies and influence of colony and ambient conditions on formic acid concentration in the hive.

    PubMed

    Ostermann, David J; Currie, Robert W

    2004-10-01

    The interaction between the effects of varroa, Varroa destructor Anderson & Trueman, and formic acid treatments on colonies of honey bees, Apis mellifera L., were examined in two field experiments. In experiment 1, colonies with low varroa levels were exposed to two different slow-release formulations and compared with untreated colonies. In experiment 2, colonies inoculated with varroa and uninoculated colonies were exposed to a slow-release formulation, a pour-on formulation, or were left untreated. The effects of treatments, hive temperature, and hive relative humidity on formic acid concentration in hive air also were examined. Slow-release formic acid application improved colony development in colonies that had been inoculated with varroa. However, in uninoculated colonies where the mean abundance of varroa was low, slow-release formic acid application suppressed colony development. The pour-on application did not have a negative impact on worker population growth in uninoculated colonies, but also it was not as effective as the slow-release treatment in improving population growth in varroa-inoculated colonies. Equivalent volumes of acid applied in pour-on and slow-release formulations provided the same cumulative dose in hive air but differed in the daily pattern of formic acid release. Colonies that were not inoculated with varroa had higher concentrations of formic acid in hive air than colonies that were inoculated with varroa on three of the five pour-on application dates. The data suggest that reductions in worker population and/or activity caused by varroa can interact with ambient conditions to affect the volatilization or sorption of formic acid in the hive. PMID:15568335

  10. Screening of Non- Saccharomyces cerevisiae Strains for Tolerance to Formic Acid in Bioethanol Fermentation

    PubMed Central

    Oshoma, Cyprian E.; Greetham, Darren; Louis, Edward J.; Smart, Katherine A.; Phister, Trevor G.; Powell, Chris; Du, Chenyu

    2015-01-01

    Formic acid is one of the major inhibitory compounds present in hydrolysates derived from lignocellulosic materials, the presence of which can significantly hamper the efficiency of converting available sugars into bioethanol. This study investigated the potential for screening formic acid tolerance in non-Saccharomyces cerevisiae yeast strains, which could be used for the development of advanced generation bioethanol processes. Spot plate and phenotypic microarray methods were used to screen the formic acid tolerance of 7 non-Saccharomyces cerevisiae yeasts. S. kudriavzeii IFO1802 and S. arboricolus 2.3319 displayed a higher formic acid tolerance when compared to other strains in the study. Strain S. arboricolus 2.3319 was selected for further investigation due to its genetic variability among the Saccharomyces species as related to Saccharomyces cerevisiae and availability of two sibling strains: S. arboricolus 2.3317 and 2.3318 in the lab. The tolerance of S. arboricolus strains (2.3317, 2.3318 and 2.3319) to formic acid was further investigated by lab-scale fermentation analysis, and compared with S. cerevisiae NCYC2592. S. arboricolus 2.3319 demonstrated improved formic acid tolerance and a similar bioethanol synthesis capacity to S. cerevisiae NCYC2592, while S. arboricolus 2.3317 and 2.3318 exhibited an overall inferior performance. Metabolite analysis indicated that S. arboricolus strain 2.3319 accumulated comparatively high concentrations of glycerol and glycogen, which may have contributed to its ability to tolerate high levels of formic acid. PMID:26284784

  11. Screening of Non- Saccharomyces cerevisiae Strains for Tolerance to Formic Acid in Bioethanol Fermentation.

    PubMed

    Oshoma, Cyprian E; Greetham, Darren; Louis, Edward J; Smart, Katherine A; Phister, Trevor G; Powell, Chris; Du, Chenyu

    2015-01-01

    Formic acid is one of the major inhibitory compounds present in hydrolysates derived from lignocellulosic materials, the presence of which can significantly hamper the efficiency of converting available sugars into bioethanol. This study investigated the potential for screening formic acid tolerance in non-Saccharomyces cerevisiae yeast strains, which could be used for the development of advanced generation bioethanol processes. Spot plate and phenotypic microarray methods were used to screen the formic acid tolerance of 7 non-Saccharomyces cerevisiae yeasts. S. kudriavzeii IFO1802 and S. arboricolus 2.3319 displayed a higher formic acid tolerance when compared to other strains in the study. Strain S. arboricolus 2.3319 was selected for further investigation due to its genetic variability among the Saccharomyces species as related to Saccharomyces cerevisiae and availability of two sibling strains: S. arboricolus 2.3317 and 2.3318 in the lab. The tolerance of S. arboricolus strains (2.3317, 2.3318 and 2.3319) to formic acid was further investigated by lab-scale fermentation analysis, and compared with S. cerevisiae NCYC2592. S. arboricolus 2.3319 demonstrated improved formic acid tolerance and a similar bioethanol synthesis capacity to S. cerevisiae NCYC2592, while S. arboricolus 2.3317 and 2.3318 exhibited an overall inferior performance. Metabolite analysis indicated that S. arboricolus strain 2.3319 accumulated comparatively high concentrations of glycerol and glycogen, which may have contributed to its ability to tolerate high levels of formic acid. PMID:26284784

  12. Spectroscopy and dynamics of double proton transfer in formic acid dimer.

    PubMed

    Mackeprang, Kasper; Xu, Zhen-Hao; Maroun, Zeina; Meuwly, Markus; Kjaergaard, Henrik G

    2016-09-21

    We present the isolated gas phase infrared spectra of formic acid dimer, (HCOOH)2, and its deuterated counterpart formic-d acid, (DCOOH)2, at room temperature. The formic acid dimer spectrum was obtained by spectral subtraction of a spectrum of formic acid vapor recorded at low pressure from that recorded at a higher pressure. The spectra of formic acid vapor contain features from both formic acid monomer and formic acid dimer, but at low and high pressures of formic acid, the equilibrium is pushed towards the monomer and dimer, respectively. A similar approach was used for the formic-d acid dimer. Building on the previous development of the Molecular Mechanics with Proton Transfer (MMPT) force field for simulating proton transfer reactions, molecular dynamics (MD) simulations were carried out to interpret the experimental spectra in the OH-stretching region. Within the framework of MMPT, a combination of symmetric single and double minimum potential energy surfaces (PESs) provides a good description of the double proton transfer PES. In a next step, potential morphing together with electronic structure calculations at the B3LYP and MP2 level of theory was used to align the computed and experimentally observed spectral features in the OH-stretching region. From this analysis, a barrier for double proton transfer between 5 and 7 kcal mol(-1) was derived, which compares with a CCSD(T)/aug-cc-pVTZ calculated barrier of 7.9 kcal mol(-1). Such a combination of experimental and computational techniques for estimating barriers for proton transfer in gas phase systems is generic and holds promise for further improved PESs and energetics of these important systems. Additional MD simulations at the semi-empirical DFTB level of theory agree quite well for the center band position but underestimate the width of the OH-stretching band. PMID:27545453

  13. High-Resolution Infrared Spectroscopy of the Formic Acid Dimer

    NASA Astrophysics Data System (ADS)

    Birer, Özgür; Havenith, Martina

    2009-05-01

    The formic acid dimer (HCOOH)2 (FAD), an eight-membered ring with double hydrogen bonds, has been a model complex for physical chemists. The acidic protons of the complex interchange between the oxygens of different units in a concerted tunneling motion. This proton tunneling can be described by a symmetric double-well potential. The double well results in a splitting of each rovibrational level. The magnitude of the splitting depends sensitively on the shape of the potential and the reduced mass along the tunneling path. Experimentally, one can determine the proton transfer tunneling splittings in the ground and vibrationally excited states separately. It is possible to work out the splitting of the energy levels, assign the correct symmetry, and obtain the sum and the difference of the tunneling splitting in the ground and vibrationally excited states independently using isotopically labeled molecules. Conversely, an accurate prediction of tunneling splitting even for this small prototype system still remains a challenge for theoretical chemistry because of the splitting's great sensitivity to the shape and barrier height of the potential surface. The FAD therefore has evolved into a prototype system to study theoretical methods for a description of proton transfer.

  14. A Direct, Biomass-Based Synthesis of Benzoic Acid: Formic Acid-Mediated Deoxygenation of the Glucose-Derived Materials Quinic Acid and Shikimic Acid

    SciTech Connect

    Arceo, Elena; Ellman, Jonathan; Bergman, Robert

    2010-05-03

    An alternative biomass-based route to benzoic acid from the renewable starting materials quinic acid and shikimic acid is described. Benzoic acid is obtained selectively using a highly efficient, one-step formic acid-mediated deoxygenation method.

  15. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  16. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  17. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  18. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  19. Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

    NASA Astrophysics Data System (ADS)

    Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-06-01

    Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

  20. Formic acid requirement for the Savannah River Site Defense Waste Processing Facility melter feed preparation

    SciTech Connect

    Hsu, C.W.

    1991-01-01

    The Westinghouse Savannah River Company (WSRC) will vitrify the high-level radioactive waste into a borosilicate glass wasteform using a slurry-fed, joule-heated melter. Formic acid is used to treat the sludge slurry for melter feed preparation. Both a minimum formate requirement and a maximum allowable formate level need to be established to adequately prepare the sludge for melter feed. The data from the Savannah River Laboratory (SRL) Scale Glass Melter (SGM), Integrated DWPF Melter System (IDMS), and research mini-melter runs were used for this purpose. The stoichiometry for major reactions during formic acid treatment was revised to reflect the more predominant chemical reactions and their yields. A minimum formic acid requirement was established according to this revised stoichiometry. Methods for determining the minimum level of formic acid were specified. An operating envelope that includes the maximum total formate level and the minimum nitrate levels, was also proposed. 5 refs., 3 figs., 4 tabs.

  1. A large and ubiquitous source of atmospheric formic acid

    NASA Astrophysics Data System (ADS)

    Millet, D. B.; Baasandorj, M.; Farmer, D. K.; Thornton, J. A.; Baumann, K.; Brophy, P.; Chaliyakunnel, S.; de Gouw, J. A.; Graus, M.; Hu, L.; Koss, A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Neuman, J. A.; Paulot, F.; Peischl, J.; Pollack, I. B.; Ryerson, T. B.; Warneke, C.; Williams, B. J.; Xu, J.

    2015-06-01

    Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2-3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx

  2. A large and ubiquitous source of atmospheric formic acid

    NASA Astrophysics Data System (ADS)

    Millet, D. B.; Baasandorj, M.; Farmer, D. K.; Thornton, J. A.; Baumann, K.; Brophy, P.; Chaliyakunnel, S.; de Gouw, J. A.; Graus, M.; Hu, L.; Koss, A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Neuman, J. A.; Paulot, F.; Peischl, J.; Pollack, I. B.; Ryerson, T. B.; Warneke, C.; Williams, B. J.; Xu, J.

    2015-02-01

    Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2-3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based: (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx:CH3OOH

  3. The Mechanism of Direct Formic Acid Fuel Cell Using Pd, Pt and Pt-Ru

    NASA Astrophysics Data System (ADS)

    Kamiya, Nobuyuki; Liu, Yan; Mitsushima, Shigenori; Ota, Ken-Ichiro; Tsutsumi, Yasuyuki; Ogawa, Naoya; Kon, Norihiro; Eguchi, Mika

    The electro-oxidation of formic acid, 2-propanol and methanol on Pd black, Pd/C, Pt-Ru/C and Pt/C has been investigated to clear the reaction mechanism. It was suggested that the formic acid is dehydrogenated on Pd surface and the hydrogen is occluded in the Pd lattice. Thus obtained hydrogen acts like pure hydrogen supplied from the outside and the cell performance of the direct formic acid fuel cell showed as high as that of a hydrogen-oxygen fuel cell. 2-propanol did not show such dehydrogenation reaction on Pd catalyst. Platinum and Pt-Ru accelerated the oxidation of C-OH of 2-propanol and methanol. Slow scan voltammogram (SSV) and chronoamperometry measurements showed that the activity of formic acid oxidation increased in the following order: Pd black > Pd 30wt.%/C > Pt50wt.%/C > 27wt.%Pt-13wt.%Ru/C. A large oxidation current for formic acid was found at a low overpotential on the palladium electrocatalysts. These results indicate that formic acid is mainly oxidized through a dehydrogenation reaction. For the oxidation of 2-propanol and methanol, palladium was not effective, and 27wt.%Pt-13wt.%Ru/C showed the best oxidation activity.

  4. Formic-acid-induced depolymerization of oxidized lignin to aromatics

    NASA Astrophysics Data System (ADS)

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.; Stahl, Shannon S.

    2014-11-01

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  5. Formic-acid-induced depolymerization of oxidized lignin to aromatics.

    PubMed

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J; Stahl, Shannon S

    2014-11-13

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered. PMID:25363781

  6. Interconversion of CO2 and formic acid by bio-inspired Ir complexes with pendent bases.

    PubMed

    Fujita, Etsuko; Muckerman, James T; Himeda, Yuichiro

    2013-01-01

    Recent investigations of the interconversion of CO2 and formic acid using Ru, Ir and Fe complexes are summarized in this review. During the past several years, both the reaction rates and catalyst stabilities have been significantly improved. Remarkably, the interconversion (i.e., reversibility) has also been achieved under mild conditions in environmentally benign water solvent by slightly changing the pH of the aqueous solution. Only a few catalysts seem to reflect a bio-inspired design such as the use of proton responsive ligands, ligands with pendent bases or acids for a second-coordination-sphere interaction, electroresponsive ligands, and/or ligands having a hydrogen bonding function with a solvent molecule or an added reagent. The most successful of these is an iridium dinuclear complex catalyst that at least has the first three of these characteristics associated with its bridging ligand. By utilizing an acid/base equilibrium for proton removal, the ligand becomes a strong electron donor, resulting in Ir(I) character with a vacant coordination site at each metal center in slightly basic solution. Complemented by DFT calculations, kinetic studies of the rates of formate production using a related family of Ir complexes with and without such functions on the ligand reveal that the rate-determining step for the CO2 hydrogenation is likely to be H2 addition through heterolytic cleavage involving a "proton relay" through the pendent base. The dehydrogenation of formic acid, owing to the proton responsive ligands changing character under slightly acidic pH conditions, is likely to occur by a mechanism with a different rate-determining step. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. PMID:23174332

  7. Effects of weaning age and formic acid-based feed additives on pigs from weaning to slaughter.

    PubMed

    Partanen, Kirsi; Siljander-Rasi, Hilkka; Pentikäinen, Jaana; Pelkonen, Sinikka; Fossi, Marja

    2007-10-01

    Two hundred and forty piglets were used in a 2 x 6 factorial experiment to study the effects of weaning age (26 or 36 d) and four formic acid-based feed additives on the performance of pigs from weaning to slaughter. Either formic acid (F) or a mixture of formic acid, propionic acid, and potassium sorbate (FPS) or a mixture of formic acid, propionic acid, and sodium benzoate (FPB) or formic acid in a diatomaceous earth carrier (FD) were added to the diets of weaned piglets (from weaning to 60 d of age) and growing (18-46 kg) and finishing pigs (46-107 kg) to provide 8, 6, and 6 g acid per kg feed, respectively. The negative control treatment's (C) diets contained no growth promoters, whereas the positive control treatment's weaner and grower diets were supplemented with 40 mg/kg of avilamycin (A). The piglets weaned at the age of 26 and 36 d weighed 7.6 and 10.7 kg at weaning (p < 0.001), and 18.5 and 17.9 kg at the age of 60 d (p > 0.05), respectively. There was a weaning age x feed additive interaction in the weight gain of piglets after weaning (p < 0.05). The weight gain of piglets weaned on day 26 was enhanced by A, FPS, and FD (p < 0.05), and that of piglets weaned on day 36 by A and FPB (p < 0.05). The feed conversion ratio was not affected by weaning ages but was decreased in groups A, F, FBS, and FPB (p < 0.05). The severity of post-weaning diarrhoea was less in groups A, F, FPS, and FD than in C (p < 0.05). In piglets weaned on day 26, faecal water content and the total Escherichia coli count were highest 9 d after weaning. The total E. coli count was reduced only by FD (p < 0.05). Increased faecal water content was characterized by increased faecal Na+ and decreased K+ concentrations. Weaning age did not influence performance or carcass quality in the growing-finishing pigs. Feed additives did not affect weight gain in the growing pigs, but FPS and FPB enhanced weight gain during finishing period and total fattening (p < 0.05). In summary, the pigs

  8. Development of a gel formulation of formic acid for control of parasitic mites of honey bees.

    PubMed

    Kochansky, J; Shimanuki, H

    1999-09-01

    Formic acid has been used in various countries for the control of parasitic mites of honey bees (Apis mellifera), particularly the Varroa mite (Varroa jacobsoni) and the tracheal mite (Acarapis woodi). Its corrosivity and consequent fear of liability have precluded commercial interest in the United States, and its rapid vaporization requires frequent reapplication. We have developed a gel formulation of formic acid which provides controlled release over 2-3 weeks and improves the convenience and safety of handling of formic acid. The strong acidity of formic acid restricts the choice of gelling agents; vegetable gellants such as agar are destroyed, and bentonite clay derivatives do not gel, even with high-shear mixing. Polyacrylamides lead to viscous liquids lacking thixotropic properties. High-molecular-weight poly(acrylic acids) and fumed silicas provided gels with suitable physical characteristics. The poly(acrylic acid) gels were difficult to mix and gave slower and nonlinear release behavior, while the fumed silica gels were easy to prepare and linear in formic acid vaporization. PMID:10552733

  9. Atmospheric geochemistry of formic and acetic acids at a mid-latitude temperate site

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Beecher, K. M.; Harriss, R. C.; Cofer, R. W., III

    1988-01-01

    Tropospheric concentrations of formic and acetic acids in the gas, the aerosol, and the rainwater phases were determined in samples collected 1-2 m above ground level at an open field site in eastern Virginia. These acids were found to occur principally (98 percent or above) in the gas phase, with a marked annual seasonality, averaging 1890 ppt for formate and 1310 ppt for acetate during the growing season, as compared to 695 ppt and 700 ppt, respectively, over the nongrowing season. The data support the hypothesis that biogenic emissions from vegatation are important sources of atmospheric formic and acetic acid during the local growing season. The same time trends were observed for precipitation, although with less defined seasonality. The relative increase of the acetic acid/formic acid ratio during the nongrowing season points to the dominance of anthropogenic inputs of acetic acid from motor vehicles and biomass combustion in the wintertime.

  10. Formic Acid Free Flowsheet Development To Eliminate Catalytic Hydrogen Generation In The Defense Waste Processing

    SciTech Connect

    Lambert, Dan P.; Stone, Michael E.; Newell, J. David; Fellinger, Terri L.; Bricker, Jonathan M.

    2012-09-14

    The Defense Waste Processing Facility (DWPF) processes legacy nuclear waste generated at the Savannah River Site (SRS) during production of plutonium and tritium demanded by the Cold War. The nuclear waste is first treated via a complex sequence of controlled chemical reactions and then vitrified into a borosilicate glass form and poured into stainless steel canisters. Converting the nuclear waste into borosilicate glass canisters is a safe, effective way to reduce the volume of the waste and stabilize the radionuclides. Testing was initiated to determine whether the elimination of formic acid from the DWPF's chemical processing flowsheet would eliminate catalytic hydrogen generation. Historically, hydrogen is generated in chemical processing of alkaline High Level Waste sludge in DWPF. In current processing, sludge is combined with nitric and formic acid to neutralize the waste, reduce mercury and manganese, destroy nitrite, and modify (thin) the slurry rheology. The noble metal catalyzed formic acid decomposition produces hydrogen and carbon dioxide. Elimination of formic acid by replacement with glycolic acid has the potential to eliminate the production of catalytic hydrogen. Flowsheet testing was performed to develop the nitric-glycolic acid flowsheet as an alternative to the nitric-formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be reduced and removed by steam stripping in DWPF with no catalytic hydrogen generation. All processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Ten DWPF tests were performed with nonradioactive simulants designed to cover a broad compositional range. No hydrogen was generated in testing without formic acid.

  11. Solid Molecular Phosphine Catalysts for Formic Acid Decomposition in the Biorefinery.

    PubMed

    Hausoul, Peter J C; Broicher, Cornelia; Vegliante, Roberta; Göb, Christian; Palkovits, Regina

    2016-04-25

    The co-production of formic acid during the conversion of cellulose to levulinic acid offers the possibility for on-site hydrogen production and reductive transformations. Phosphorus-based porous polymers loaded with Ru complexes exhibit high activity and selectivity in the base-free decomposition of formic acid to CO2 and H2 . A polymeric analogue of 1,2-bis(diphenylphosphino)ethane (DPPE) gave the best results in terms of performance and stability. Recycling tests revealed low levels of leaching and only a gradual decrease in the activity over seven runs. An applicability study revealed that these catalysts even facilitate selective removal of formic acid from crude product mixtures arising from the synthesis of levulinic acid. PMID:27043017

  12. Highly conductive PEDOT:PSS treated with formic acid for ITO-free polymer solar cells.

    PubMed

    Mengistie, Desalegn A; Ibrahem, Mohammed A; Wang, Pen-Cheng; Chu, Chih-Wei

    2014-02-26

    We proposed a facile film treatment with formic acid to enhance the conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) by 4 orders of magnitude. The effect of formic acid concentration on conductivity was investigated; conductivity increased fast with increasing concentration up to 10 M and then increased slightly, the highest conductivity being 2050 S cm(-1) using 26 M concentration. Formic acid treated PEDOT:PSS films also exhibited very high transmittances. The mechanism of conductivity enhancement was explored through SEM, AFM, and XPS. Formic acid with its high dielectric constant screens the charge between PEDOT and PSS bringing about phase separation between them. Increased carrier concentration, removal of PSS from the film, morphology, and conformation change with elongated and better connected PEDOT chains are the main mechanisms of conductivity enhancement. ITO-free polymer solar cells were also fabricated using PEDOT:PSS electrodes treated with different concentrations of formic acid and showed equal performance to that of ITO electrodes. The concentrated acid treatment did not impair the desirable film properties as well as stability and performance of the solar cells. PMID:24460075

  13. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

    PubMed Central

    Kawasaki, Shin-ichiro; Suzuki, Akira

    2013-01-01

    Summary The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

  14. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors.

    PubMed

    Javaid, Rahat; Kawasaki, Shin-Ichiro; Suzuki, Akira; Suzuki, Toshishige M

    2013-01-01

    The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd-Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

  15. Anchoring the gas-phase acidity scale: From formic acid to methanethiol

    NASA Astrophysics Data System (ADS)

    Eyet, Nicole; Villano, Stephanie M.; Bierbaum, Veronica M.

    2009-06-01

    We have measured the gas-phase acidities of nine compounds: formic acid, acetic acid, 1,3-propanedithiol, 2-methyl-2-propanethiol, 3-methyl-1-butanethiol, 2-propanethiol, 1-propanethiol, ethanethiol, and methanethiol, with acidities ranging from 338.6 to 351.1 kcal mol-1 using proton transfer kinetics and the resulting equilibrium constants. These acids were anchored to the well-known acidity of hydrogen sulfide; the measured acidities are in good agreement with previous experimental values, but error bars are significantly reduced. The gas-phase acidity of 3-methyl-1-butanethiol was determined to be 347.1 (5) kcal mol-1; there were no previous measurements of this value. Entropies of deprotonation were calculated and enthalpies of deprotonation were determined.

  16. FTIR Studies of the Photochemistry of Deuterated Formic Acid in a Parahydrogen Matrix

    NASA Astrophysics Data System (ADS)

    Anderson, David T.

    2014-06-01

    We report new FTIR studies of the 193 nm photochemistry of deuterated formic acid (DCOOD) trapped in parahydrogen matrices. In our 2011 preliminary report, we showed the 193 nm in situ photolysis of formic acid (HCOOH) produces small amounts of HCO and HOCO and that after the laser is turned off, we observe continued slow growth in the HOCO radical for up to 10 hours after photolysis. At that time we were unsure of the detailed chemical mechanism by which the HOCO continues to grow after photolysis, but we suspected it had to do with reactions of mobile H-atoms with the HCOOH precursor that remains at significant concentrations after photolysis under these conditions. The present deuterated formic acid photolysis studies provide strong circumstantial evidence that H-atom reactions with formic acid are the source of the continued HOCO growth. Further, variable-temperature kinetic studies conducted with the deuterated formic acid sample show a strong inverse temperature dependence to the reaction kinetics. Essentially, the reaction that leads to HOCO growth only occurs at temperatures below 2.4 K. We are currently trying to model the kinetics using standard methods and the most recent analysis will be presented at the meeting. David T. Anderson, Leif O. Paulson, 66th Ohio State University International Symposium on Molecular Spectroscopy, talk FE02 (2011).

  17. Coke-free direct formic acid solid oxide fuel cells operating at intermediate temperatures

    NASA Astrophysics Data System (ADS)

    Chen, Yubo; Su, Chao; Zheng, Tao; Shao, Zongping

    2012-12-01

    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.

  18. A new product with formic acid for Varroa jacobsoni Oud. control in Argentina. I. Efficacy.

    PubMed

    Eguaras, M; Del Hoyo, M; Palacio, M A; Ruffinengo, S; Bedascarrasbure, E L

    2001-02-01

    An organic product based on formic acid in a gel matrix was evaluated for use in Varroa control under autumnal climatic conditions in Argentina. Twenty colonies each received two gel packets with formic acid in two applications and numbers of falling mites were registered. After this treatment colonies received two other acaricides in order to compare efficacy. Average final efficacy in colonies treated with the organic product was 92% with a low variability. The gel matrix kept an adequate formic acid concentration inside the colonies with only two applications. This product is, therefore, a good alternative for Varroa control because it is organic, easy to use and presents a low variability in final efficacy between colonies. No queen, brood, or adult honeybee mortality was registered. PMID:11254094

  19. Facile synthesis of PtAu alloy nanoparticles with high activity for formic acid oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Yin, Geping; Lin, Yuehe

    2010-02-15

    We report the facile synthesis of carbon supported PtAu alloy nanoparticles with high electrocatalytic activity as the anode catalyst for direct formic acid fuel cells (DFAFCs). PtAu alloy nanopaticles are synthesized by co-reducing HAuCl4 and H2PtCl6 with NaBH4 in the presence of sodium citrate and then the nanoparticles are deposited on Vulcan XC-72R carbon support (PtAu/C). The obtained catalysts are characterized with X-ray diffraction (XRD) and transmission electron microscope (TEM), which reveal PtAu alloy formation with an average diameter of 4.6 nm. PtAu/C exhibits 8 times higher catalytic activity toward formic acid oxidation than Pt/C. The enhanced activity of PtAu/C catalyst is attributed to noncontinuous Pt sites formed in the presence of the neighbored Au sites, which promotes direct oxidation of formic acid by avoiding poison CO.

  20. Suicidal carbon monoxide poisoning by combining formic acid and sulfuric acid within a confined space.

    PubMed

    Lin, Peter T; Dunn, William A

    2014-01-01

    Suicide by inhalation of carbon monoxide produced by mixing formic acid and sulfuric acid within a confined space is a rare method of suicide. This method is similar to the so-called "detergent suicide" method where an acid-based detergent is mixed with a sulfur source to produce hydrogen sulfide. Both methods produce a toxic gas that poses significant hazards for death investigators, first responders and bystanders. Carbon monoxide is an odorless gas, while hydrogen sulfide has a characteristic rotten eggs odor, so the risks associated with carbon monoxide are potentially greater due to lack of an important warning signal. While detergent suicides have become increasingly common in the USA, suicide with formic acid and sulfuric acid is rare with only three prior cases being reported. Greater awareness of this method among death investigators is warranted because of the special risks of accidental intoxication by toxic gas and the possibility that this method of suicide will become more common in the future. PMID:24328850

  1. Scanning electrochemical microscopy: surface interrogation of adsorbed hydrogen and the open circuit catalytic decomposition of formic acid at platinum.

    PubMed

    Rodríguez-López, Joaquín; Bard, Allen J

    2010-04-14

    The surface interrogation mode of scanning electrochemical microscopy (SECM) is extended to the in situ quantification of adsorbed hydrogen, H(ads), at polycrystalline platinum. The methodology consists of the production, at an interrogator electrode, of an oxidized species that is able to react with H(ads) on the Pt surface and report the amounts of this adsorbate through the SECM feedback response. The technique is validated by comparison to the electrochemical underpotential deposition (UPD) of hydrogen on Pt. We include an evaluation of electrochemical mediators for their use as oxidizing reporters for adsorbed species at platinum; a notable finding is the ability of tetramethyl-p-phenylenediamine (TMPD) to oxidize (interrogate) H(ads) on Pt at low pH (0.5 M H(2)SO(4) or 1 M HClO(4)) and with minimal background effects. As a case study, the decomposition of formic acid (HCOOH) in acidic media at open circuit on Pt was investigated. Our results suggest that formic acid decomposes at the surface of unbiased Pt through a dehydrogenation route to yield H(ads) at the Pt surface. The amount of H(ads) depended on the open circuit potential (OCP) of the Pt electrode at the time of interrogation; at a fixed concentration of HCOOH, a more negative OCP yielded larger amounts of H(ads) until reaching a coulomb limiting coverage close to 1 UPD monolayer of H(ads). The introduction of oxygen into the cell shifted the OCP to more positive potentials and reduced the quantified H(ads); furthermore, the system was shown to be chemically reversible, as several interrogations could be run consecutively and reproducibly regardless of the path taken to reach a given OCP. PMID:20225806

  2. Transformation of cellulose and its derived carbohydrates into formic and lactic acids catalyzed by vanadyl cations.

    PubMed

    Tang, Zhenchen; Deng, Weiping; Wang, Yanliang; Zhu, Enze; Wan, Xiaoyue; Zhang, Qinghong; Wang, Ye

    2014-06-01

    The transformation of cellulose or cellulose-derived carbohydrates into platform chemicals is the key to establish biomass-based sustainable chemical processes. The systems able to catalyze the conversion of cellulose into key chemicals in water without the consumption of hydrogen are limited. We report that simple vanadyl (VO(2+)) cations catalyze the conversions of cellulose and its monomer, glucose, into lactic acid and formic acid in water. We have discovered an interesting shift of the major product from formic acid to lactic acid on switching the reaction atmosphere from oxygen to nitrogen. Our studies suggest that VO(2+) catalyzes the isomerization of glucose to fructose, the retro-aldol fragmentation of fructose to two trioses, and the isomerization of trioses, which leads to the formation of lactic acid under anaerobic conditions. The oxidative cleavage of C-C bonds in the intermediates caused by the redox conversion of VO2(+)/VO(2+) under aerobic conditions results in formic acid and CO2. We demonstrate that the addition of an alcohol suppresses the formation of CO2 and enhances the formic acid yield significantly to 70-75 %. PMID:24798653

  3. A large underestimate of the pyrogenic source of formic acid inferred from space-borne measurements.

    NASA Astrophysics Data System (ADS)

    Chaliyakunnel, S.; Millet, D. B.; Wells, K. C.; Cady-Pereira, K.; Shephard, M.

    2015-12-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere, and a dominant source of acidity in the global troposphere. Recent work has revealed a major gap in our present understanding of the atmospheric formic acid budget, with observed concentrations much larger than can be reconciled with current estimates of its sources. In this work, we employ new space-based observations from the Tropospheric Emission Spectrometer (TES) satellite instrument with the GEOS-Chem chemical transport model to better quantify the source of atmospheric formic acid from biomass burning, and assess the degree to which this source can help close the large budget gap for this species. The space-based formic acid data reveal a severe model underestimate for HCOOH that is most prominent over tropical biomass burning regions, indicating a major missing source of organic acids from fires. Based on two independent methods for inferring the fractional contribution of fires to the measured HCOOH abundance, we find that the pyrogenic HCOOH:CO enhancement ratio measured by TES (including direct emissions plus secondary production) is 5-10 times higher than current estimates of the direct emission ratio, providing evidence of substantial secondary production of HCOOH in fire plumes. We further show that current models significantly underestimate (by a factor of 2-6) the total primary and secondary source of HCOOH from tropical fires.

  4. Oxidation mechanism of formic acid on the bismuth adatom-modified Pt(111) surface.

    PubMed

    Perales-Rondón, Juan Victor; Ferre-Vilaplana, Adolfo; Feliu, Juan M; Herrero, Enrique

    2014-09-24

    In order to improve catalytic processes, elucidation of reaction mechanisms is essential. Here, supported by a combination of experimental and computational results, the oxidation mechanism of formic acid on Pt(111) electrodes modified by the incorporation of bismuth adatoms is revealed. In the proposed model, formic acid is first physisorbed on bismuth and then deprotonated and chemisorbed in formate form, also on bismuth, from which configuration the C-H bond is cleaved, on a neighbor Pt site, yielding CO2. It was found computationally that the activation energy for the C-H bond cleavage step is negligible, which was also verified experimentally. PMID:25188779

  5. Formic acid as a hydrogen storage material - development of homogeneous catalysts for selective hydrogen release.

    PubMed

    Mellmann, Dörthe; Sponholz, Peter; Junge, Henrik; Beller, Matthias

    2016-07-11

    Formic acid (FA, HCO2H) receives considerable attention as a hydrogen storage material. In this respect, hydrogenation of CO2 to FA and dehydrogenation of FA are crucial reaction steps. In the past decade, for both reactions, several molecularly defined and nanostructured catalysts have been developed and intensively studied. From 2010 onwards, this review covers recent advancements in this area using homogeneous catalysts. In addition to the development of catalysts for H2 generation, reversible H2 storage including continuous H2 production from formic acid is highlighted. Special focus is put on recent progress in non-noble metal catalysts. PMID:27119123

  6. Detection of formic acid in the cold, dark cloud L134N

    NASA Technical Reports Server (NTRS)

    Irvine, W. M.; Minh, Y. C.; Friberg, P.; Kaifu, N.; Matthews, H. E.

    1990-01-01

    The detection of formic acid (HCOOH) in a cold dark interstellar cloud (L134N) is reported. The observed abundance of 3 x 10 to the 10th relative to H2 is between one and two orders of magnitude lower than that calculated by published ion-molecule models of dark-cloud chemistry, but is quite consistent with recent model revisions based on new reaction rates. Formic acid was not detected in the archetypical dark cloud TMC-1, and was tentatively detected in the region of massive star formation W51.

  7. A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid.

    PubMed

    Qi, Xinxin; Li, Chong-Liang; Wu, Xiao-Feng

    2016-04-18

    Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source. PMID:26934464

  8. Copper corrosion mechanism in the presence of formic acid vapor for short exposure times

    SciTech Connect

    Bastidas, J.M.; Lopez-Delgado, A.; Cano, E.; Polo, J.L.; Lopez, F.A.

    2000-03-01

    The rate of copper corrosion originated by the action of formic acid vapors at 100% relative humidity was studied. Five formic vapor concentration levels (10, 50, 100, 200, and 300 ppm) were used. A copper corrosion rate of up to 1,300 mg/m{sup 2} d was measured for a period of 21 days using a gravimetric method. The patina layers were characterized using cathodic reduction, X-ray powder diffraction. Fourier transform infrared spectrometry, and scanning electron microscopy techniques. Some of the components identified in the corrosion-product layers were cuprite (Cu{sub 2}O), cupric hydroxide hydrate [Cu(OH){sub 2}{sm_bullet}H{sub 2}O], and copper formate hydrate [Cu(HCOO){sub 2}{sm_bullet}4H{sub 2}O]. The latter was formed by both cupric hydroxide and formic acid-cuprous ion complex mechanisms.

  9. Pd nanoparticles supported on functionalized multi-walled carbon nanotubes (MWCNTs) and electrooxidation for formic acid

    NASA Astrophysics Data System (ADS)

    Yang, Sudong; Zhang, Xiaogang; Mi, Hongyu; Ye, Xiangguo

    To improve the utilization and activity of anodic catalysts for formic acid electrooxidation, palladium (Pd) particles were loaded on the MWCNTs, which were functionalized in a mixture of 96% sulfuric acid and 4-aminobenzenesulfonic acid, using sodium nitrite to produce intermediate diazonium salts from substituted anilines. The composition, particle size, and crystallinity of the Pd/f-MWCNTs catalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and energy dispersive spectroscopy (EDS) measurements. The electrocatalytic properties of the Pd/f-MWCNTs catalysts for formic acid oxidation were investigated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) in 0.5 mol L -1 H 2SO 4 solution. The results demonstrated that the catalytic activity was greatly enhanced due to the improved water-solubility and dispersion of the f-MWCNTs, which were facile to make the small particle size (3.8 nm) and uniform dispersion of Pd particles loading on the surface of the MWCNTs. In addition, the functionalized MWCNTs with benzenesulfonic group can provide benzenesulfonic anions in aqueous solution, which may combine with hydrogen cation and then promote the oxidation of formic acid reactive intermediates. So the Pd/f-MWCNTs composites showed excellent electrocatalytic activity for formic acid oxidation.

  10. Interactions between Carboxylic Acids and Heteroaromatics: A Rotational Study of Formic Acid-Pyridine.

    PubMed

    Spada, Lorenzo; Gou, Qian; Giuliano, Barbara M; Caminati, Walther

    2016-07-14

    The rotational spectra of four isotopologues of the 1:1 complex between formic acid and pyridine show that the two units are linked together through a "classical" (OH···N) and a weak (CH···O) hydrogen bond. The molecular system appears quite rigid and no effects of the internal motions have been observed in the spectrum. The dissociation energy obtained from the centrifugal distortion by applying an approximate model, 39.8 kJ/mol, is quite similar to the ab initio value, 41.7 kJ/mol. Its relatively high value suggests a small charge transfer to take place. PMID:26886392

  11. Influence of sodium carbonate on decomposition of formic acid by pulsed discharge plasma inside bubble in water

    NASA Astrophysics Data System (ADS)

    Iwabuchi, Masashi; Takahashi, Katsuyuki; Takaki, Koichi; Satta, Naoya

    2016-07-01

    The influence of sodium carbonate on the decomposition of formic acid by discharge inside bubbles in water was investigated experimentally. Oxygen or argon gases were injected into the water through a vertically positioned glass tube, in which the high-voltage wire electrode was placed to generate plasmas at low applied voltage. The concentration of formic acid was determined by ion chromatography. In the case of sodium carbonate additive, the pH increased owing to the decomposition of the formic acid. In the case of oxygen injection, the percentage of conversion of formic acid increased with increasing pH because the reaction rate of ozone with formic acid increased with increasing pH. In the case of argon injection, the percentage of conversion was not affected by the pH owing to the high rate loss of hydroxyl radicals.

  12. A vibrational study of the adsorption and decomposition of formic acid and surface formate on Al(111)

    NASA Astrophysics Data System (ADS)

    Crowell, J. E.; Chen, J. G.; Yates, J. T., Jr.

    1986-09-01

    The adsorption and decomposition of formate and formic acid have been studied on the Al(111) surface using high resolution electron energy loss spectroscopy (EELS) and temperature programmed desorption (TPD). Formic acid reacts with clean Al(111) at 120 K to form a surface formate species. Molecular adsorption of formic acid occurs at 120 K only after saturation of the surface formate layer has been reached. Off-specular vibrational measurements have determined that the formate species is symmetrically bridge bonded through both oxygen atoms with C2v symmetry. A lower symmetry formate species of C1 symmetry is produced upon heating or electron bombardment of a condensed formic acid layer. Thermal or electron induced decomposition of a formate or a condensed formic acid layer is controlled by oxygen incorporation into the aluminum lattice, and results in complete decomposition and production of a carbon and oxygen covered surface. Only hydrogen is evolved from a formate-covered Al(111) surface.

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

    PubMed Central

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

    2012-01-01

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

  14. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Formic acid; exemption from the requirement of a tolerance. 180.1178 Section 180.1178 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Exemptions From Tolerances § 180.1178...

  15. 76 FR 7106 - Food Additives Permitted in Feed and Drinking Water of Animals; Formic Acid

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-09

    ... notice published in the Federal Register of December 7, 2009 (74 FR 64091), FDA announced that a food... agent in swine feed. This action is in response to a food additive petition filed by Kemira Oyj of... safe use of formic acid as an acidifying agent at levels not to exceed 1.2 percent in swine feed....

  16. A [NiFe]hydrogenase model that catalyses the release of hydrogen from formic acid.

    PubMed

    Nguyen, Nga T; Mori, Yuki; Matsumoto, Takahiro; Yatabe, Takeshi; Kabe, Ryota; Nakai, Hidetaka; Yoon, Ki-Seok; Ogo, Seiji

    2014-11-11

    We report the decomposition of formic acid to hydrogen and carbon dioxide, catalysed by a NiRu complex originally developed as a [NiFe]hydrogenase model. This is the first example of H2 evolution, catalysed by a [NiFe]hydrogenase model, which does not require additional energy. PMID:25234420

  17. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

    SciTech Connect

    Lee, H.; Habas, S.E.; Somorjai, G.A.; Yang, P.

    2008-03-20

    Binary Pt/Pd nanoparticles were synthesized by localized overgrowth of Pd on cubic Pt seeds for the investigation of electrocatalytic formic acid oxidation. The binary particles exhibited much less self-poisoning and a lower activation energy relative to Pt nanocubes, consistent with the single crystal study.

  18. Characterization and formic acid oxidation studies of PtAu nanoparticles.

    PubMed

    Saipanya, Surin; Srisombat, Laongnuan; Wongtap, Pitak; Sarakonsri, Thapanee

    2014-10-01

    Characterization and electrocatalytic oxidation of formic acid on PtAu nanoparticles supported multiwalled carbon nanotube (MWCNT) were studied. Electrochemical measurements were conducted in a self-made conventional three-electrode glass cell at room temperature. A Pt wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. The Pt was electrodeposited onto the electrode and their catalytic activities in the electrooxidation of formic acid were examined and compared. The morphology and composition were studied by a combination of transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). Cyclic voltamograms of formic acid electrooxidation show a distinguishing shape with a prominent oxidation peak in the forward scan contributed to the formic acid oxidation whilst the backward scan is associated with the oxidation of exclusion of carbonaceous species. On the basis of the onset potential and current density, the resulting PtAu nanoparticles showed much higher electrocatalytic activity than other counterparts. The results show an excellent sign of applications for fuel cell. PMID:25942921

  19. Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods.

    PubMed

    Liu, Chao; Li, Bin; Du, Haishun; Lv, Dong; Zhang, Yuedong; Yu, Guang; Mu, Xindong; Peng, Hui

    2016-10-20

    In this work, nanocellulose was extracted from bleached corncob residue (CCR), an underutilized lignocellulose waste from furfural industry, using four different methods (i.e. sulfuric acid hydrolysis, formic acid (FA) hydrolysis, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and pulp refining, respectively). The self-assembled structure, morphology, dimension, crystallinity, chemical structure and thermal stability of prepared nanocellulose were investigated. FA hydrolysis produced longer cellulose nanocrystals (CNCs) than the one obtained by sulfuric acid hydrolysis, and resulted in high crystallinity and thermal stability due to its preferential degradation of amorphous cellulose and lignin. The cellulose nanofibrils (CNFs) with fine and individualized structure could be isolated by TEMPO-mediated oxidation. In comparison with other nanocellulose products, the intensive pulp refining led to the CNFs with the longest length and the thickest diameter. This comparative study can help to provide an insight into the utilization of CCR as a potential source for nanocellulose production. PMID:27474618

  20. Effect of formic acid or formaldehyde treatment of alfalfa silage on nutrient utilization by dairy cows.

    PubMed

    Nagel, S A; Broderick, G A

    1992-01-01

    Third-cutting alfalfa with 37% DM was ensiled untreated or treated with either 2.8 g of formic acid/100 g of DM or .31 g of formaldehyde/100 g of DM and fed to lactating dairy cows in two experiments. Silage treated with formic acid had the lowest pH and concentrations of NPN, NH3, and total free AA. Both treatments decreased rumen in vitro protein degradability but did not affect in vitro rumen plus pepsin digestibility. In trial 1, part 1, 22 Holstein cows received a standard diet for 18 d postpartum and then were fed for 6 wk one of three diets containing 98% alfalfa silage DM. Although DMI was comparable, yields of milk, SCM, fat, protein, lactose, and SNF were higher when treated silages were fed. Plasma concentrations of branched-chain, essential, and total AA increased when formic acid-treated silage was fed. Rumen pH and concentrations of NH3 and VFA were similar for all diets. Rumen escape protein, estimated using 15N as a microbial protein marker, was increased more by formic acid than by formaldehyde treatment. In trial 1, part 2, supplementation with 4.8% fish meal increased concentration of milk protein and yields of milk, protein, lactose, and SNF. Milk urea concentration was higher on the untreated silage diet. Total tract apparent DM and N digestibilities were not affected by silage treatment, although fish meal decreased apparent DM digestibility. In trial 2, 80:20 alfalfa silage:ground corn diets were fed to 12 midlactation cows in a 3 x 3 Latin square study. Milk production was unaffected, but milk protein concentration and DMI were higher when treated silages were fed. Feeding treated silages increased plasma concentrations of branched-chain AA, essential AA, and total AA. Formaldehyde and especially formic acid treatment effectively improved utilization of nutrients in alfalfa silage by lactating dairy cows. PMID:1541728

  1. Microwave Spectroscopy and Proton Transfer Dynamics in the Formic Acid-Acetic Acid Dimer

    NASA Astrophysics Data System (ADS)

    Howard, B. J.; Steer, E.; Page, F.; Tayler, M.; Ouyang, B.; Leung, H. O.; Marshall, M. D.; Muenter, J. S.

    2012-06-01

    The rotational spectrum of the doubly hydrogen-bonded {hetero} dimer formed between formic acid and acetic acid has been recorded between 4 and 18 GHz using a pulsed-nozzle Fourier transform microwave spectrometer. Each rigid-molecule rotational transition is split into four as a result of two concurrent tunnelling motions, one being proton transfer between the two acid molecules, and the other the torsion/rotation of the methyl group within the acetic acid. We present a full assignment of the spectrum for {J} = 1 to {J} = 7 for these four torsion/tunnelling states. Spectra have been observed for the main isotopic species, with deuterium substitution at the C of the formic acid and all 13C species in natural abundance, The observed transitions are fitted to within a few kilohertz using a molecule-fixed effective rotational Hamiltonian for the separate {A} and {E} vibrational species of the G12 permutation-inversion group which is applicable to this complex. To reduce the effects of internal angular momentum, a non-principal axis system is used throughout. Interpretation of the internal motion uses an internal-vibration and overall rotation scheme, and full sets of rotational and centrifugal distortion constants are determined. The proton tunnelling rates and the internal angular momentum of the methyl group in the {E} states is interpreted in terms of a dynamical model which involves coupled proton transfer and internal rotation. The resulting potential energy surface not only describes these internal motions, but can also explain the observed shifts in rotational constants between {A} and {E} species, and the deviations of the tunnelling frequencies from the expected 2:1 ratio. It also permits the determination of spectral constants free from the contamination effects of the internal dynamics. M.C.D. Tayler, B. Ouyang and B.J. Howard, J. Chem. Phys., {134}, 054316 (2011).

  2. Technical and economical assessment of formic acid to recycle phosphorus from pig slurry by a combined acidification-precipitation process.

    PubMed

    Daumer, M-L; Picard, S; Saint-Cast, P; Dabert, P

    2010-08-15

    Dissolution by acidification followed by a liquid/solid separation and precipitation of phosphorus from the liquid phase is one possibility to recycle phosphorus from livestock effluents. To avoid increase of effluent salinity by using mineral acids in the recycling process, the efficiency of two organic acids, formic and acetic acid, in dissolving the mineral phosphorus from piggery wastewater was compared. The amount of formic acid needed to dissolve the phosphorus was reduced three fold, compared to acetic acid. The amount of magnesium oxide needed for further precipitation was decreased by two with formic acid. Neither the carbon load nor the effluent salinity was significantly increased by using formic acid. An economical comparison was performed for the chemical recycling process (mineral fertilizer) vs. centrifugation (organic fertilizer) considering the centrifugation and the mineral fertilizers sold in the market. After optimisation of the process, the product could be economically competitive with mineral fertilizer as superphosphate in less than 10 years. PMID:20471746

  3. Analysis of the stable carbon isotope composition of formic and acetic acids.

    PubMed

    Lee, Xinqing; Zhang, Like; Huang, Daikuan; An, Ning; Yang, Fang; Jiang, Wei; Fang, Bin

    2013-05-15

    Formic and acetic acids are ubiquitous in the environment and in many biological processes. Analysis of the stable carbon isotope composition (δ(13)C) of formic and acetic acids is important to understanding their biogeochemical cycles. However, it has been faced with poor accuracy and high detection limits due to their low carbon number, high hydrophilicity, and semi-volatility. Here we developed an analytical technique by needle trap and gas chromatography-isotope ratio mass spectrometry (GC-IRMS). The organic acids in aqueous solution were extracted using a NeedlEx needle through purge-and-trap and were analyzed by GC-IRMS for δ(13)C. The procedures incur no isotope fractionation. Defined as the point at which the mean δ(13)C is statistically the same as the given value and the analytical error starts rising, the method's detection limits are 200 and 100 mg/L for formic and acetic acids, respectively, with an uncertainty of approximately 0.5‰ in direct extraction and analysis. They were lowered to 1 mg/L with precision of 0.9‰ after samples were subjected to preconcentration. The method was successfully applied to natural samples as diverse as precipitation, vinegars, ant plasma, and vehicle exhaust, which vary considerably in concentration and matrix of the organic acids. It is applicable to the organic acids in not only aqueous solution but also gaseous phase. PMID:23395975

  4. Adsorption and thermal chemistry of formic acid on clean and oxygen-predosed Cu(110) single-crystal surfaces revisited

    NASA Astrophysics Data System (ADS)

    Yao, Yunxi; Zaera, Francisco

    2016-04-01

    The thermal chemistry of formic acid on clean and oxygen-predosed Cu(110) single-crystal surfaces was studied under ultrahigh-vacuum (UHV) conditions by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Key results reported in the past were confirmed, including the partial switchover from H2 to H2O desorption upon oxygen addition on the surface and the development of a second decomposition regime at 420 K, in addition to the one observed at 460 K on the clean substrate. In addition, new observations were added, including the previously missed desorption of H2 at 420 K and the existence of a normal kinetic isotope effect in both TPD peaks. Peak fitting of the XPS data afforded the identification of an asymmetric geometry for the formate intermediate, which was established to form by 200 K, and the presence of coadsorbed molecular formic acid up to the temperatures of decomposition, probably in a second layer and held by hydrogen bonding. Quantitative analysis of the TPD data indicated a one-to-one correspondence between the increase in oxygen coverage beyond θO = 0.5 ML and a decrease in formic acid uptake that mainly manifests itself in a decrease in the decomposition seen in the 460 K TPD peak. All these observations were interpreted in terms of a simple decomposition mechanism involving hydrogen abstraction from adsorbed formate species, possibly aided by coadsorbed oxygen, and a change in reaction activation energy as a function of the structure of the oxygen overlayer, which reverts from a O-c(6 × 2) structure at high oxygen coverages to the O-(2 × 1) order seen at θO = 0.5 ML.

  5. Formic and acetic acid over the central Amazon region, Brazil 1. Dry season

    SciTech Connect

    Andreae, M.O.; Talbot, R.W.; Andreae, T.W.; Harriss, R.C.

    1988-02-20

    We have determined the atmospheric concentrations of formic and acetic acid in the gas phase, in aerosols, and in rain during the dry season (July--August 1985) in the Amazonia region of Brazil. At ground level the average concentrations of gas phase formic and acetic acid were 1.6 +- 0.6 and 2.2 +- 1.0 ppb, respectively. The diurnal behavior of both acids at ground level and their vertical distribution in the forest canopy point to the existence of vegetative sources as well as to production by chemical reactions in the atmosphere. Dry deposition of the gaseous acids appears to be a major sink. The concentrations of formic and acetic acid in the gas phase were about 2 orders of magnitude higher than concentrations of the corresponding species in the atmospheric aerosol. About 50--60%/sub 0/ of the aerosol (total) formate and acetate were in the size fraction below 1.0 ..mu..m diameter.

  6. The vertical transmission of salmonellas and formic acid treatment of chicken feed. A possible strategy for control.

    PubMed Central

    Humphrey, T. J.; Lanning, D. G.

    1988-01-01

    The treatment of feed given to laying hens with 0.5% formic acid reduced significantly the isolation rate of salmonellas and was associated with a reduction in the incidence of infection in newly hatched chicks. These improvements were not sustained until slaughter, however, as growing birds acquired salmonellas, probably from feed which was not acid treated. The data indicate that formic acid treatment of chicken food could have important benefits for the public health. PMID:3338506

  7. Electrocatalytic oxidation of formic acid at an ordered intermetallic PtBi surface.

    PubMed

    Casado-Rivera, Emerilis; Gál, Zoltán; Angelo, A C D; Lind, Cora; DiSalvo, Francis J; Abruña, Héctor D

    2003-02-17

    The electrocatalytic oxidation of formic acid at a PtBi ordered intermetallic electrode surface has been investigated using cyclic voltammetry, rotating disk electrode (RDE) voltammetry and differential electrochemical mass spectrometry (DEMS). The results are compared to those at a polycrystalline platinum electrode surface. The PtBi electrode exhibits superior properties when compared to polycrystalline platinum in terms of oxidation onset potential, current density, and a much diminished poisoning effect by CO. Using the RDE technique, a value of 1.4 x 10(-4) cm s-1 was obtained for the heterogeneous charge transfer rate constant. The PtBi surface did not appear to be poisoned when exposed to a CO saturated solution for periods exceeding 0.5 h. The results for PtBi are discussed within the framework of the dual-path mechanism for the electrocatalytic oxidation of formic acid, which involves formation of a reactive intermediate and a poisoning pathway. PMID:12619419

  8. Synthesis and assembly of Pd nanoparticles on graphene for enhanced electrooxidation of formic acid

    NASA Astrophysics Data System (ADS)

    Jin, Tao; Guo, Shaojun; Zuo, Jing-Lin; Sun, Shouheng

    2012-12-01

    Monodisperse 4.5 nm Pd nanoparticles (NPs) were synthesized by solution phase reduction of palladium acetylacetonate with morpholine borane in a mixture of oleylamine and 1-octadecene. These NPs were assembled on graphene uniformly in the form of a monolayer, and showed much enhanced catalysis for electrooxidation of formic acid. The work demonstrates the great potential of graphene as a support to enhance NP catalysis and stability for important chemical oxidation reactions.Monodisperse 4.5 nm Pd nanoparticles (NPs) were synthesized by solution phase reduction of palladium acetylacetonate with morpholine borane in a mixture of oleylamine and 1-octadecene. These NPs were assembled on graphene uniformly in the form of a monolayer, and showed much enhanced catalysis for electrooxidation of formic acid. The work demonstrates the great potential of graphene as a support to enhance NP catalysis and stability for important chemical oxidation reactions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33060a

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

    PubMed

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

    2014-09-22

    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

  10. Formic acid-based treatments for control of Varroa destructor in a Mediterranean area.

    PubMed

    Satta, Alberto; Floris, Ignazio; Eguaras, Martin; Cabras, Paolo; Garau, Vincenzo Luigi; Melis, Marinella

    2005-04-01

    Two formic acid autumnal treatments, gel packets (BeeVar formulation) and impregnated paperwick (Liebig-Dispenser), were tested in apiary to evaluate their effectiveness against Varroa destructor Anderson & Trueman and their residues in honey in a Mediterranean region (Sardinia, Italy). Both treatments were efficient in the apiary control of the varroosis, with values of percentage of mite mortality ranging between 93.6 and 100%, without statistical differences between them. The more gradual release of formic acid from the gel application allowed a longer action (2 wk for each treatment) compared with the Liebig-Dispenser (approximately 3d for each treatment). The rate of daily evaporation ranged between approximately 5 and 9 g/d from BeeVar and approximately 26 and 35 g/d from the Liebig-Dispenser, in the first and second treatment, respectively. The total amount of formic acid administered per hive during all the treatment period was approximately 200 g for either treatment. A significantly higher adult bee mortality was recorded in the Liebig-Dispenser-treated hives compared with the BeeVar-treated group. On the contrary, BeeVar treatment produced an interruption of brood reared, whereas the extension of the sealed brood area of the Liebig-Dispenser-treated hives was not significantly different from that of the control hives. Neither queen mortality nor robbing activity was observed due to the treatments. Formic acid residues in honey collected in the nest were 3,855 +/- 2,061 and 3,030 +/- 1,624 mg/kg for the BeeVar- and the Liebig-Dispenser-treated hives, respectively. After 21 d from the end of the treatment, the residues fell to 1,261 +/- 1,054 and 794 +/- 518 mg/kg for the honey sampled from the BeeVar and Liebig-Dispenser groups, respectively. PMID:15889712

  11. One site is enough: a theoretical investigation of iron-catalyzed dehydrogenation of formic Acid.

    PubMed

    Sánchez-de-Armas, Rocío; Xue, Liqin; Ahlquist, Mårten S G

    2013-09-01

    Dehydrogenation of HCO2H: The reaction mechanism for the dehydrogenation of formic acid catalyzed by a highly active and selective iron complex has been studied by DFT. The most favorable pathway shows the hydride in Fe-H complexes acting as a spectator ligand throughout the catalytic cycle. This result opens up the Fe complex for modification in order to achieve more efficient and selective catalysts. PMID:23907850

  12. Performance characterization of Pd/C nanocatalyst for direct formic acid fuel cells

    NASA Astrophysics Data System (ADS)

    Ha, S.; Larsen, R.; Masel, R. I.

    Previous work has demonstrated that unsupported Pd (Pd black) based direct formic acid fuel cells (DFAFCs) show unusually high power density at the ambient temperature. In this paper finely dispersed Pd particles have been deposited on carbon supports (Vulcan XC-72 ®). In particular, both 20 and 40 wt.% Pd on carbon supports (Pd/C) nanocatalysts have been synthesized and their performances, as an anode catalyst for DFAFC, with different formic acid feed concentrations at a moderate temperature have been evaluated. The 20 and 40 wt.% Pd/C based DFAFCs, with dry air and zero backpressure, can generate a maximum power density of 145 and 172 mW cm -2 at 30 °C, respectively. Their open cell potentials are 0.90 V. In comparison to the unsupported Pd, we found that the 20 wt.% Pd/C in the DFAFC shows a lower total current, but a higher current per gram of precious metal than the Pd black catalyst. The supported catalysts also show less deactivation at the high formic acid concentrations.

  13. Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications.

    PubMed

    Jiang, Kun; Zhang, Han-Xuan; Zou, Shouzhong; Cai, Wen-Bin

    2014-10-14

    Formic acid as a natural biomass and a CO2 reduction product has attracted considerable interest in renewable energy exploitation, serving as both a promising candidate for chemical hydrogen storage material and a direct fuel for low temperature liquid fed fuel cells. In addition to its chemical dehydrogenation, formic acid oxidation (FAO) is a model reaction in the study of electrocatalysis of C1 molecules and the anode reaction in direct formic acid fuel cells (DFAFCs). Thanks to a deeper mechanistic understanding of FAO on Pt and Pd surfaces brought about by recent advances in the fundamental investigations, the "synthesis-by-design" concept has become a mainstream idea to attain high-performance Pt- and Pd-based nanocatalysts. As a result, a large number of efficient nanocatalysts have been obtained through different synthesis strategies by tailoring geometric and electronic structures of the two primary catalytic metals. In this paper, we provide a brief overview of recent progress in the mechanistic studies of FAO, the synthesis of novel Pd- and Pt-based nanocatalysts as well as their practical applications in DFAFCs with a focus on discussing studies significantly contributing to these areas in the past five years. PMID:25144896

  14. CO2 Hydrogenation to Formic Acid on Ni(111)

    SciTech Connect

    Peng, Guowen; Sibener, S. J.; Schatz, George C.; Ceyer, Sylvia T.; Mavrikakis, Manos

    2011-12-26

    Periodic, self-consistent, density functional theory (DFT) calculations are employed to study CO2 hydrogenation on Ni(111). CO2 hydrogenation with H adsorbed on the surface and with H absorbed in the subsurface is investigated systematically, and the respective microscopic reaction mechanisms are elucidated. We show that on Ni(111) CO2 hydrogenation to formate intermediate is more favorable than to carboxyl intermediate. The hydrogenation to formate goes through the unidentate structure that rapidly transforms into the bidentate structure. Further hydrogenation from formate to formic acid is energetically more difficult than formate formation. Formation of adsorbed formic acid from adsorbed CO2 and surface hydrogen is an endothermic reaction. Because subsurface H in Ni(111) is substantially less stable compared to surface H, its reaction with adsorbed CO2 to adsorbed formic acid is an exothermic one. Finally, our results may have significant implications for the synthesis of liquid fuels from CO2 and for catalytic hydrogenation reactions in general.

  15. DISSOCIATIVE RECOMBINATION OF PROTONATED FORMIC ACID: IMPLICATIONS FOR MOLECULAR CLOUD AND COMETARY CHEMISTRY

    SciTech Connect

    Vigren, E.; Hamberg, M.; Zhaunerchyk, V.; Larsson, M.; Thomas, R. D.; Af Ugglas, M.; Kashperka, I.; Geppert, W. D.; Kaminska, M.; Semaniak, J.; Millar, T. J.; Walsh, C.; Roberts, H.

    2010-02-01

    At the heavy ion storage ring CRYRING in Stockholm, Sweden, we have investigated the dissociative recombination of DCOOD{sup +}{sub 2} at low relative kinetic energies, from approx1 meV to 1 eV. The thermal rate coefficient has been found to follow the expression k(T) = 8.43 x 10{sup -7} (T/300){sup -0.78} cm{sup 3} s{sup -1} for electron temperatures, T, ranging from approx10 to approx1000 K. The branching fractions of the reaction have been studied at approx2 meV relative kinetic energy. It has been found that approx87% of the reactions involve breaking a bond between heavy atoms. In only 13% of the reactions do the heavy atoms remain in the same product fragment. This puts limits on the gas-phase production of formic acid, observed in both molecular clouds and cometary comae. Using the experimental results in chemical models of the dark cloud, TMC-1, and using the latest release of the UMIST Database for Astrochemistry improves the agreement with observations for the abundance of formic acid. Our results also strengthen the assumption that formic acid is a component of cometary ices.

  16. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

    SciTech Connect

    Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter A.; Li, Sha; Mavrikakis, Manos

    2014-12-05

    We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

  17. Liquids in the Diamond Anvil Cell: High Pressure-Temperature Chemistry of Formic Acid

    NASA Astrophysics Data System (ADS)

    Montgomery, W. B.; Zaug, J. M.; Goncharov, A. F.; Howard, W. M.; Manaa, M. R.; Jeanloz, R.; Young, C. E.; Crowhurst, J. C.

    2003-12-01

    The chemical and physical properties of liquids under high pressures and temperatures are of continuing interest and application to the planetary science community. Using near-simultaneous FTIR and Raman spectroscopy including high-resolution optical video, we have begun to study the behavior of formic acid (HCOOH) at conditions observed on Europa, Ganymede and Callisto. We present a phase diagram, including melting curve, proposed reaction mechanisms and solid-state phase transitions, over a temperature range from 300-550 K and a pressure range from .1 to 9 GPa. Reaction products, including CO2 and amorphous carbons (COOHn) have been identified. Preliminary results from FTIR studies are used to determine reaction rates, and pressure dependent activation energies. We have also employed a detailed kinetic reaction mechanism to study the decomposition of formic acid at extreme conditions by using a fluid exponential-6 equation-of-state for the reacting species. We have used first principles DFT and semi-empirical tight binding methods to predict properties of solid formic acid under isotropic and uniaxial compression. We compare the results of both simulations to our experimental observations.

  18. Matrix isolation infrared and ab initio study of the hydrogen bonding between formic acid and water

    NASA Astrophysics Data System (ADS)

    George, Lisa; Sander, Wolfram

    2004-11-01

    The infrared spectra of the formic acid-water complexes isolated in argon matrices are reported. Both supersonic jet expansion and a conventional effusive source followed by trapping in solid argon at 10 K are used to obtain the matrices. The experimental IR spectra are compared to the data obtained from high level ab initio (MP2) and DFT (B3LYP) calculations with 6-311++G(d,p) and aug-cc-pVTZ basis sets. The complex formation results in red shifts in the CO and OH stretching vibrations and a blue shift in the CO stretching vibration of formic acid. The OH stretching modes of water also exhibit pronounced red shifts. Both the MP2 and B3LYP calculations located three minima corresponding to cyclic HCOOH⋯H 2O complexes with two hydrogen bond interactions. The binding energies are -10.3, -5.1, and -3.5 kcal mol -1, respectively, for the three complexes at the MP2/ aug-cc-pVTZ level, corrected for the basis set superposition error (BSSE) using the Boys-Bernardi counterpoise scheme. Comparison of the calculated frequencies of the three complexes with the matrix IR spectrum reveals that the lowest energy complex is formed. In addition, a complex of formic acid with two water molecules is observed.

  19. One-pot transformation of cellobiose to formic acid and levulinic acid over ionic-liquid-based polyoxometalate hybrids.

    PubMed

    Li, Kaixin; Bai, Linlu; Amaniampong, Prince Nana; Jia, Xinli; Lee, Jong-Min; Yang, Yanhui

    2014-09-01

    Currently, levulinic acid (LA) and formic acid (FA) are considered as important carbohydrates for the production of value-added chemicals. Their direct production from biomass will open up a new opportunity for the transformation of biomass resource to valuable chemicals. In this study, one-pot transformation of cellobiose into LA and FA was demonstrated, using a series of multiple-functional ionic liquid-based polyoxometalate (IL-POM) hybrids as catalytic materials. These IL-POMs not only markedly promoted the production of valuable chemicals including LA, FA and monosaccharides with high selectivities, but also provided great convenience of the recovery and the reuse of the catalytic materials in an environmentally friendly manner. Cellobiose conversion of 100%, LA selectivity of 46.3%, and FA selectivity of 26.1% were obtained at 423 K and 3 MPa for 3 h in presence of oxygen. A detailed catalytic mechanism for the one-pot transformation of cellobiose was also presented. PMID:25110998

  20. Hydrogen from formic acid through its selective disproportionation over sodium germanate--a non-transition-metal catalysis system.

    PubMed

    Amos, Ruth I J; Heinroth, Falk; Chan, Bun; Zheng, Sisi; Haynes, Brian S; Easton, Christopher J; Masters, Anthony F; Radom, Leo; Maschmeyer, Thomas

    2014-10-13

    A robust catalyst for the selective dehydrogenation of formic acid to liberate hydrogen gas has been designed computationally, and also successfully demonstrated experimentally. This is the first such catalyst not based on transition metals, and it exhibits very encouraging performance. It represents an important step towards the use of renewable formic acid as a hydrogen-storage and transport vector in fuel and energy applications. PMID:25169798

  1. Hydrolysis of ketene catalyzed by formic acid: modification of reaction mechanism, energetics, and kinetics with organic acid catalysis.

    PubMed

    Louie, Matthew K; Francisco, Joseph S; Verdicchio, Marco; Klippenstein, Stephen J; Sinha, Amitabha

    2015-05-14

    The hydrolysis of ketene (H2C═C═O) to form acetic acid involving two water molecules and also separately in the presence of one to two water molecules and formic acid (FA) was investigated. Our results show that, while the currently accepted indirect mechanism, involving addition of water across the carbonyl C═O bond of ketene to form an ene-diol followed by tautomerization of the ene-diol to form acetic acid, is the preferred pathway when water alone is present, with formic acid as catalyst, addition of water across the ketene C═C double bond to directly produce acetic acid becomes the kinetically favored pathway for temperatures below 400 K. We find not only that the overall barrier for ketene hydrolysis involving one water molecule and formic acid (H2C2O + H2O + FA) is significantly lower than that involving two water molecules (H2C2O + 2H2O) but also that FA is able to reduce the barrier height for the direct path, involving addition of water across the C═C double bond, so that it is essentially identical with (6.4 kcal/mol) that for the indirect ene-diol formation path involving addition of water across the C═O bond. For the case of ketene hydrolysis involving two water molecules and formic acid (H2C2O + 2H2O + FA), the barrier for the direct addition of water across the C═C double bond is reduced even further and is 2.5 kcal/mol lower relative to the ene-diol path involving addition of water across the C═O bond. In fact, the hydrolysis barrier for the H2C2O + 2H2O + FA reaction through the direct path is sufficiently low (2.5 kcal/mol) for it to be an energetically accessible pathway for acetic acid formation under atmospheric conditions. Given the structural similarity between acetic and formic acid, our results also have potential implications for aqueous-phase chemistry. Thus, in an aqueous environment, even in the absence of formic acid, though the initial mechanism for ketene hydrolysis is expected to involve addition of water across the

  2. Microwave spectra and structure of the cyclopropanecarboxylic acid-formic acid dimer.

    PubMed

    Pejlovas, Aaron M; Lin, Wei; Kukolich, Stephen G

    2015-09-28

    The rotational spectrum of the cyclopropanecarboxylic acid-formic acid doubly hydrogen bonded dimer has been measured in the 4-11 GHz region using a Flygare-Balle type pulsed-beam Fourier transform microwave spectrometer. Rotational transitions were measured for the parent, four unique singly substituted (13)C isotopologues, and a singly deuterated isotopologue. Splittings due to a possible concerted double proton tunneling motion were not observed. Rotational constants (A, B, and C) and centrifugal distortion constants (DJ and DJK) were determined from the measured transitions for the dimer. The values of the rotational (in MHz) and centrifugal distortion constants (in kHz) for the parent isotopologue are A = 4045.4193(16), B = 740.583 80(14), C = 658.567 60(23), DJ = 0.0499(16), and DJK = 0.108(14). A partial gas phase structure of the dimer was derived from the rotational constants of the measured isotopologues, previous structural work on each monomer units and results of the calculations. PMID:26429015

  3. Microwave spectra and structure of the cyclopropanecarboxylic acid-formic acid dimer

    NASA Astrophysics Data System (ADS)

    Pejlovas, Aaron M.; Lin, Wei; Kukolich, Stephen G.

    2015-09-01

    The rotational spectrum of the cyclopropanecarboxylic acid-formic acid doubly hydrogen bonded dimer has been measured in the 4-11 GHz region using a Flygare-Balle type pulsed-beam Fourier transform microwave spectrometer. Rotational transitions were measured for the parent, four unique singly substituted 13C isotopologues, and a singly deuterated isotopologue. Splittings due to a possible concerted double proton tunneling motion were not observed. Rotational constants (A, B, and C) and centrifugal distortion constants (DJ and DJK) were determined from the measured transitions for the dimer. The values of the rotational (in MHz) and centrifugal distortion constants (in kHz) for the parent isotopologue are A = 4045.4193(16), B = 740.583 80(14), C = 658.567 60(23), DJ = 0.0499(16), and DJK = 0.108(14). A partial gas phase structure of the dimer was derived from the rotational constants of the measured isotopologues, previous structural work on each monomer units and results of the calculations.

  4. Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways

    NASA Astrophysics Data System (ADS)

    Le Breton, Michael; Bacak, Asan; Muller, Jennifer B. A.; Xiao, Ping; Shallcross, Beth M. A.; Batt, Rory; Cooke, Michael C.; Shallcross, Dudley E.; Bauguitte, S. J.-B.; Percival, Carl J.

    2014-02-01

    The first simultaneous measurements of formic and nitric acid mixing ratios around the United Kingdom were measured on the FAAM BAe-146 research aircraft with a chemical ionization mass spectrometer using I- reagent ions at 0.8 Hz. Analysis of the whole dataset shows that formic acid and nitric acid are positively correlated as illustrated by other studies (e.g. Veres et al., 2011). However, initial evidence indicates a prominent direct source of formic acid and also a significant source when O3 levels are high, suggesting the importance of the ozonolysis of 1-alkenes. A trajectory model was able to reproduce the formic acid concentrations by both the inclusion of a primary vehicle source and production via ozonolysis of propene equivalent 1-alkene levels. Inspection of data archives implies these levels of 1-alkene are possible after 11 am, but formic acid and nitric acid plumes early in the flight are too high for the model to replicate. These data show the relationship between nitric acid and formic acid cannot solely be attributed to related photochemical production. The simultaneous measurement of HCOOH and HNO3 has been implemented to estimate OH levels along the flight track assuming a relationship between formic and nitric acid in photochemical plumes and a constant source of 1-alkene.

  5. Efficient Reduction of CO2 into Formic Acid on a Lead or Tin Electrode using an Ionic Liquid Catholyte Mixture.

    PubMed

    Zhu, Qinggong; Ma, Jun; Kang, Xinchen; Sun, Xiaofu; Liu, Huizhen; Hu, Jiayin; Liu, Zhimin; Han, Buxing

    2016-07-25

    Highly efficient electrochemical reduction of CO2 into value-added chemicals using cheap and easily prepared electrodes is environmentally and economically compelling. The first work on the electrocatalytic reduction of CO2 in ternary electrolytes containing ionic liquid, organic solvent, and H2 O is described. Addition of a small amount of H2 O to an ionic liquid/acetonitrile electrolyte mixture significantly enhanced the efficiency of the electrochemical reduction of CO2 into formic acid (HCOOH) on a Pb or Sn electrode, and the efficiency was extremely high using an ionic liquid/acetonitrile/H2 O ternary mixture. The partial current density for HCOOH reached 37.6 mA cm(-2) at a Faradaic efficiency of 91.6 %, which is much higher than all values reported to date for this reaction, including those using homogeneous and noble metal electrocatalysts. The reasons for such high efficiency were investigated using controlled experiments. PMID:27311592

  6. Formic and acetic acid over the central Amazon region, Brazil. I - Dry season

    NASA Technical Reports Server (NTRS)

    Andreae, M. O.; Andreae, T. W.; Talbot, R. W.; Harriss, R. C.

    1988-01-01

    The concentrations of formic and acetic acids in the gas phase, atmospheric aerosol, and rainwater samples collected in Amazonia at ground level and in the atmosphere during the Amazon Boundary Layer Experiment in July/August 1985 were analyzed by ion exchange chromatography. The diurnal behavior of both acids at ground level and their vertical distribution in the forest canopy point to the existence of vegetative sources as well as to production by chemical reactions in the atmosphere. The concentrations of formic and acetic acids in the gas phase were about 2 orders of magnitude higher than the corresponding concentrations in the atmospheric aerosol. In rainwater, the total formate and acetate represented about one half of the anion equivalents, in contrast to less than 10 percent of the soluble anionic equivalents contributed by these acids in the atmospheric aerosol. The observed levels of these ions in rainwater are considered to be the result of a combination of chemical reactions in hydrometeors and the scavenging of the gaseous acids by cloud droplets.

  7. Microwave spectra and structure of the cyclopropanecarboxylic acid-formic acid dimer

    SciTech Connect

    Pejlovas, Aaron M.; Kukolich, Stephen G.; Lin, Wei

    2015-09-28

    The rotational spectrum of the cyclopropanecarboxylic acid–formic acid doubly hydrogen bonded dimer has been measured in the 4-11 GHz region using a Flygare-Balle type pulsed-beam Fourier transform microwave spectrometer. Rotational transitions were measured for the parent, four unique singly substituted {sup 13}C isotopologues, and a singly deuterated isotopologue. Splittings due to a possible concerted double proton tunneling motion were not observed. Rotational constants (A, B, and C) and centrifugal distortion constants (D{sub J} and D{sub JK}) were determined from the measured transitions for the dimer. The values of the rotational (in MHz) and centrifugal distortion constants (in kHz) for the parent isotopologue are A = 4045.4193(16), B = 740.583 80(14), C = 658.567 60(23), D{sub J} = 0.0499(16), and D{sub JK} = 0.108(14). A partial gas phase structure of the dimer was derived from the rotational constants of the measured isotopologues, previous structural work on each monomer units and results of the calculations.

  8. Indoor winter fumigation with formic acid for control of Acarapis woodi (Acari: Tarsonemidae) and nosema disease, Nosema sp.

    PubMed

    Underwood, Robyn M; Currie, Robert W

    2009-10-01

    Indoor fumigation of honey bees, Apis mellifera L., with formic acid to control varroa mites, Varroa destructor Anderson & Trueman, allows simultaneous fumigation of multiple colonies with little labor input and good efficacy. Several experiments were designed to test the efficacy of formic acid as a treatment for honey bee mites, Acarapis woodi (Rennie) (Acari: Tarsonemidae), and nosema disease, Nosema sp., indoors in winter. The objectives of this study were (1) to determine the efficacy of formic acid fumigation for honey bee mite control by using both the thoracic slice and live dissection methods and (2) to determine whether indoor fumigation can reliably prevent the buildup of nosema disease in overwintering honey bee colonies. Indoor winter fumigation of honey bee colonies with formic acid was effective in killing a high percentage of honey bee mites but did not significantly reduce the proportion of bees with infested tracheae over the duration of the experiments. Thus, the method used to determine the efficacy of the treatment affected the results. Under conditions of relatively low or decreasing levels of nosema, fumigation tended to suppress the mean abundance of nosema spores relative to the controls. In three separate fumigation experiments using a range of formic acid concentrations, there was no statistical difference between the buildup or maintenance of nosema spore mean abundance over the winter in bees from formic acid fumigated colonies compared with untreated controls. However, fumigation with formic acid during winter at a low concentration for extended periods significantly suppressed spore buildup of mixed populations of nosema (Nosema apis and Nosema ceranae) in 1 yr. PMID:19886435

  9. Hydrogen evolution from formic acid in an ionic liquid solvent: a mechanistic study by ab initio molecular dynamics.

    PubMed

    Bhargava, B L; Yasaka, Yoshiro; Klein, Michael L

    2011-12-01

    The reversible decomposition of formic acid (HCOOH ⇌ CO(2) + H(2)) has been attracting attention for its potential utility in hydrogen storage and production. It is therefore of interest to explore the influence of solvents on the decomposition reaction. To this end, Born-Oppenheimer (BO) molecular dynamics (MD) calculations have been performed to explore the mechanism involved in hydrogen (H(2)) evolution from formic acid decomposition in an ionic liquid solvent. Specifically, for a solvent consisting of 1,3-dimethylimidazolium cations and formate anions, evolution of hydrogen (H(2)) and carbon dioxide (CO(2)) was observed within a few picoseconds when BO-MD trajectories were carried out at an elevated temperature of 3000 K. The observed dehydrogenation involved a reaction between a formic acid solute and a nearby solvent formate anion. The observed mechanism contrasts with the unimolecular mechanism proposed in the gas phase. Specifically, in the ionic liquid, the reaction is initiated from a C-H bond dissociation of a formate anion to produce a short-lived hydride anion, which subsequently captures the acidic proton of a nearby formic acid molecule. The present BO-MD computations suggest that the high reducing ability of formic acid in the ionic liquid is due in part to its acid-dissociated form: the formate anion, which is encouraged to dissociate into a hydride anion and CO(2) by the strong electrostatic field of the ionic liquid solvent. PMID:21774513

  10. Carbon disulfide-formic acid: an efficient desorbant for industrial solvents

    SciTech Connect

    Raulinaitis, I.

    1987-11-01

    When vapors of one solvent are collected on a charcoal tube, the desorbants suggested by NIOSH are adequate. When several solvents are collected at the same time, however, then a desorbant suggested for one solvent may mask some of the analytes or some of the analytes may be desorbed very poorly. An actual sample containing 13 solvents was brought to the laboratory for analysis. All solvents could be resolved on a 6-m 10% FFAP column, but some could not be desorbed efficiently with carbon disulfide; masking problems were encountered with other desorbants. Several solvents were tried; the most promising one was carbon disulfide saturated with formic acid.

  11. Formic acid dehydrogenation catalysed by ruthenium complexes bearing the tripodal ligands triphos and NP3.

    PubMed

    Mellone, Irene; Peruzzini, Maurizio; Rosi, Luca; Mellmann, Dörthe; Junge, Henrik; Beller, Matthias; Gonsalvi, Luca

    2013-02-21

    The selective formic acid dehydrogenation to a mixture of CO(2) and H(2) was achieved with moderate to good productivities in the presence of homogeneous Ru catalysts bearing the polydentate tripodal ligands 1,1,1-tris-(diphenylphosphinomethyl)ethane (triphos) and tris-[2-(diphenylphosphino)ethyl]amine (NP(3)), either made in situ from suitable Ru(III) precursors or as molecular complexes. Preliminary mechanistic studies highlighting subtle differences due to ligand effects in the corresponding systems under study are also presented. PMID:23212285

  12. Direct synthesis of graphene nanosheets support Pd nanodendrites for electrocatalytic formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Yang, Su-Dong; Chen, Lin

    2015-11-01

    We report a solvothermal method preparation of dendritic Pd nanoparticles (DPNs) and spherical Pd nanoparticles (SPNs) supported on reduced graphene oxide (RGO). Drastically different morphologies of Pd NPs with nanodendritic structures or spherical structures were observed on graphene by controlling the reduction degree of graphene oxide (GO) under mild conditions. In addition to being a commonplace substrate, GO plays a more important role that relies on its surface groups, which serves as a shape-directing agent to direct the dendritic growth. As a result, the obtained DPNs/RGO catalyst exhibits a significantly enhanced electro-catalytic behavior for the oxidation of formic acid compared to the SPNs/RGO catalyst.

  13. Shape of the Adduct Formic Acid-Dimethyl Ether: A Rotational Study.

    PubMed

    Evangelisti, Luca; Spada, Lorenzo; Li, Weixing; Ciurlini, Anna; Grabow, Jens-Uwe; Caminati, Walther

    2016-05-12

    Formic acid and dimethyl ether are combined in a supersonic expansion to form a molecular adduct with the two subunits held together by a "classical" OH···O hydrogen bond and a bifurcated weak CH2···O hydrogen bond. The rotational spectra of the parent and of two (13)C isotopologues in natural abundance show that the complex has Cs symmetry, with the heavy atom symmetry planes of HCOOH and (CH3)2O perpendicular to each other. PMID:27102727

  14. Sources and sinks of formic, acetic, and pyruvic acids over central Amazonia. II - Wet season

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Andreae, M. O.; Berresheim, H.; Jacob, D. J.; Beecher, K. M.

    1990-01-01

    Potential sources and sinks of formic, acetic, and pyruvic acids over the Amazon forest were investigated using a photochemical model and data collected on gas phase concentrations of these acids in the forest canopy, boundary layer, and free troposphere over the central Amazon Basin during the 1987 wet season. It was found that the atmospheric reactions previously suggested in the literature as sources of carboxylic acids (i.e., the gas phase decomposition of isoprene, the reaction between CH3CO3 and a peroxide, and aqueous phase oxidation of CH2O) appear to be too slow to explain the observed concentrations, suggesting that other atmospheric reactions, so far unidentified, could make a major contribution to the carboxylic acid budgets.

  15. Selective conversion of organic pollutant p-chlorophenol to formic acid using zeolite Fenton catalyst.

    PubMed

    Shen, Chensi; Ma, Jianqing; Liu, Wanpeng; Wen, Yuezhong; Rashid, Sadia

    2016-10-01

    Effective remediation technologies which can converse the harmful organic pollutants to high-value chemicals are crucial both for wastewater treatment and energy regeneration. This study provides an evidence that extracting useful chemicals from wastewater is feasible through selective conversion of p-chlorophenol to high value formic acid as an example. The reported system works with a readily available Fe-containing ZSM-5 catalyst, water as the solvent and hydrogen peroxide as the oxidant. The yield of formic acid reached up to 50.7% when the Si/Al ratio of ZSM-5 was 80 and the Fe-content was 1.4%. By X-ray adsorption fine structure (XAFS), NH3 temperature-programmed desorption (NH3-TPD) technique, the pyridine adsorption Fourier-transition infrared (Py-IR) spectroscopy and adsorption measurements, it was concluded that the controllable degradation of p-CP could be approached through selective adsorption, the moderate Brønsted acid sites for H2O2 activation and the properly selective conversion control due to extra-framework coordination unsaturated sites (CUS) of Fe. This approach might provide a new avenue for the field of organic pollutant remediation. PMID:27459155

  16. Oxidation of formic acid on platinum surfaces decorated with cobalt(III) macrocyclic complexes

    NASA Astrophysics Data System (ADS)

    Stevanović, S.; Babić-Samardžija, K.; Sovilj, S. P.; Tripković, A.; Jovanović, V. M.

    2009-09-01

    Platinum electrode decorated with three different mixed-ligand cobalt(III) complexes of the general formula [Co(Rdtc)cyclam](ClO4)2 [cyclam = 1,4,8,11-tetraazacyclotetradecane, Rdtc- = morpholine-(Morphdtc), piperidine-(Pipdtc), and 4-methylpiperidine-(4-Mepipdtc) dithiocarbamates, respectively] was used to study oxidation of formic acid in acidic solution. The complexes were adsorbed on differently prepared Pt surfaces, at open circuit potential. The preliminary results show increased catalytic activity of Pt for formic acid oxidation with complex ion adsorbed on the polycrystalline surfaces. The increase in catalytic activity depends on the structure of the complex applied and follows the order of metal-coordinated bidentate ligand as Morphdtc > Pipdtc > 4-Mepipdtc. Based on IR and NMR data, the main characteristics of the Rdtc ligands do not vary dramatically, but high symmetry of the corresponding complexes decreases in the same order. Accordingly, the complexes are distinctively more mobile, causing chemical interactions to occur on the surface with appreciable speed and enhanced selectivity. The effect of the complexes on catalytic activity presumably depends on structural changes on Pt surfaces caused by their adsorption.

  17. The Partitioning of Acetic, Formic, and Phosphoric Acids Between Liquid Water and Steam

    SciTech Connect

    Gruszkiewicz, M.S.; Marshall, S.L.; Palmer, D.A.; Simonson, J.M.

    1999-06-22

    The chemical carryover of impurities and treatment chemicals from the boiler to the steam phase, and ultimately to the low-pressure turbine and condenser, can be quantified based on laboratory experiments preformed over ranges of temperature, pH, and composition. The two major assumptions are that thermodynamic equilibrium is maintained and no deposition, adsorption or decomposition occurs. The most recent results on acetic, formic and phosphoric acids are presented with consideration of the effects of hydrolysis and dimerization reactions. Complications arising from thermal decomposition of the organic acids are discussed. The partitioning constants for these acids and other solutes measured in this program have been incorporated into a simple thermodynamic computer code that calculates the effect of chemical and mechanical carryover on the composition of the condensate formed to varying extents in the water/steam cycle.

  18. Elevated formic acid concentrations in putrefied post-mortem blood and urine samples.

    PubMed

    Viinamäki, Jenni; Rasanen, Ilpo; Vuori, Erkki; Ojanperä, Ilkka

    2011-05-20

    Formic acid (FA) concentration was measured in post-mortem blood and urine samples as methyl formate using a headspace in-tube extraction gas-chromatography-mass-spectrometry method. A total of 113 cases were analyzed, each including a blood and urine sample fortified with 1% sodium fluoride. The cases were divided into three groups: regular (n=59), putrefied (n=30), and methanol-positive (n=22) cases. There was no evidence of ante-mortem methanol consumption in the regular and putrefied cases. In regular cases, the mean (and median) FA concentrations were 0.04 g/l (0.04 g/l) and 0.06 g/l (0.04 g/l) in blood and urine, respectively. In putrefied cases, the mean (and median) FA concentrations were substantially higher, 0.24 g/l (0.22 g/l) and 0.25 g/l (0.15 g/l) in blood and urine, respectively. In three putrefied cases, FA concentration in blood exceeded 0.5 g/l, a level associated with fatal methanol poisoning. Ten putrefied cases were reanalyzed after 3-4 months storage, and no significant changes in FA concentrations were seen. These observations suggest that FA was formed by putrefaction during the post-mortem period, not during sample storage when sodium fluoride was added as a preservative. In methanol-positive cases, the mean (and median) FA concentrations were 0.80 g/l (0.88 g/l) and 3.4 g/l (3.3 g/l) in blood and urine, respectively, and the concentrations ranged from 0.19 to 1.0 g/l in blood and from 1.7 to 5.6 g/l in urine. The mean (and median) methanol concentrations in methanol-positive cases were 3.0 g/l (3.0 g/l) and 4.4 g/l (4.7 g/l) in blood and in urine, respectively. The highest methanol concentrations were 6.0 g/l and 8.7 g/l in blood and urine, respectively. No ethyl alcohol was found in the methanol-positive blood samples. Poor correlation was shown between blood and urine concentrations of FA. Poor correlations were also shown, in both blood and urine, between methanol and FA concentrations. PMID:21112705

  19. Formic acid microfluidic fuel cell based on well-defined Pd nanocubes

    NASA Astrophysics Data System (ADS)

    Moreno-Zuria, A.; Dector, A.; Arjona, N.; Guerra-Balcázar, M.; Ledesma-García, J.; Esquivel, J. P.; Sabaté, N.; Arrriaga, L. G.; Chávez-Ramírez, A. U.

    2013-12-01

    Microfluidic fuel cells (μFFC) are emerging as a promising solution for small-scale power demands. The T-shaped architecture of the μFFC promotes a laminar flow regimen between the catholyte and anolyte streams excluding the use of a membrane, this property allows a simplest design and the use of several micromachining techniques based on a lab-on-chip technologies. This work presents a combination of new materials and low cost fabrication processes to develop a light, small, flexible and environmental friendly device able to supply the energy demand of some portable devices. Well-defined and homogeneous Pd nanocubes which exhibited the (100) preferential crystallographic plane were supported on Vulcan carbon and used as anodic electrocatalyst in a novel and compact design of a SU-8 μFFC feeded with formic acid as fuel. The SU-8 photoresist properties and the organic microelectronic technology were important factors to reduce the dimensions of the μFFC structure. The results obtained from polarization and power density curves exhibited the highest power density (8.3 mW cm-2) reported in literature for direct formic acid μFFCs.

  20. Formic acid electrooxidation on Bi-modified polyoriented and preferential (111) Pt nanoparticles.

    PubMed

    López-Cudero, Ana; Vidal-Iglesias, Francisco J; Solla-Gullón, José; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2009-01-14

    Formic acid electrooxidation was studied on Bi modified polyoriented and preferential (111) Pt nanoparticles. For both types of nanoparticles, Bi coverage was progressively increased and its effect on formic acid electrooxidation was evaluated using cyclic voltammetry and chronoamperometric measurements. In both experiments, significant and progressive enhancements on the electrooxidation current densities were obtained in comparison to the bare Pt nanoparticles. In voltammetry, at maximum Bi coverage, higher current densities at peak potential were obtained with the preferential (111) Pt nanoparticles (approximately 42 mA cm(-2)) as compared to the polyoriented Pt nanoparticles (approximately 32 mA cm(-2)) in agreement with previous single crystal studies. Nevertheless, this tendency was not observed in chronoamperometry at 0.4 V where currents obtained at maximum Bi coverage were similar. On the other hand, CO poison formation was also evaluated at open circuit potential. The resulting electrochemical activity has been rationalized using different parameters, such as surface structure, size domains, particle size and Bi coverage. PMID:19088999

  1. Hydrogen bonding in the hydroxysulfinyl radical-formic acid-water system: A theoretical study.

    PubMed

    Tušar, Simona; Lesar, Antonija

    2016-06-30

    Quantum chemical methods have been employed to evaluate the possible configurations of the 1:1 and 1:2 HOSO-formic acid complexes and 1:1:1 HOSO-formic acid-water complexes. The first type of complex involves two H bonds, while the other two types comprise three H bonds in a ring. The complexes are relatively stable, with CBS-QB3 computed binding energies of 14.3 kcal mol(-1) , 23.4 kcal mol(-1) , and 21.1 kcal mol(-1) for the lowest-energy structures of the 1:1, 1:2, and 1:1:1 complexes, respectively. Complex formations induce a large spectral red-shift and an enhancement of the IR intensity for the H-bonded OH stretching modes relative to those in the parent monomers. TDDFT calculations of the low-lying electronic excited states demonstrate that the complexes are photochemically quite stable in the troposphere. Small spectral shifts in comparison to the free HOSO radical suggest that the radical and the complexes would not be easily distinguishable using standard UV/vis absorption spectroscopy. © 2016 Wiley Periodicals, Inc. PMID:27074890

  2. Hydrogenation of CO2 to formic acid over a Cu-embedded graphene: A DFT study

    NASA Astrophysics Data System (ADS)

    Sirijaraensre, J.; Limtrakul, J.

    2016-02-01

    DFT calculations were used to investigate the properties of the atomic copper embedded in the surface of graphene (Cu/dG) and the catalytic reaction pathway for the CO2 hydrogenation to formic acid (FA). The Cu/dG was active for the adsorption of the hydrogen molecule (H2), and provided a reaction site for the heterolytic cleavage of H2, leading to the formation of Cu-H deposited on a singly hydrogenated vacancy graphene (Cu-H/H-dG). The protonation of CO2 takes place facilely over the generated metal-hydride species (Cu-H). Under the dilution of H2, the catalytic process would be hampered by the formation of copper-formate deposited on the H-dG due mainly to the very high energy demand for the transformation of the copper-formate to FA through the protonation from the H-dG. It was further found that the presence of H2 in the system plays a significant role in producing the FA on the Cu/dG catalyst. The copper-formate species can be converted into formic acid via the heterolytic cleavage of the second hydrogen molecule, yielding the FA and Cu-H species.

  3. Effective fall treatment of Varroa jacobsoni (Acari: Varroidae) with a new formulation of formic acid in colonies of Apis mellifera (Hymenoptera: Apidae) in the northeastern United States.

    PubMed

    Calderone, N W

    2000-08-01

    New formulations of formic acid and thymol, both individually and in combination with various essential oils, were compared with Apistan to determine their efficacy as fall treatments for control of Varroa jacobsoni (Oudemans), a parasitic mite of the honey bee, Apis mellifera L. Percent mite mortality in colonies treated with 300 ml of 65% formic acid averaged 94.2 +/- 1.41% (least square means +/- SE, n = 24), equivalent to those receiving four, 10% strips of Apistan (92.6 +/- 1.79%, n = 6). Treatment with thymol (n = 24) resulted in an average mite mortality of 75.4 +/- 5.79%, significantly less than that attained with Apistan or formic acid. The addition of essential oils did not affect treatment efficacy of either formic acid or thymol. The ratio of the coefficients of variation for percentage mortality for the formic acid (CVFA) and Apistan (CVA) groups was CVFA/CVA = 0.66. This indicates that the formic acid treatment was as consistent as the Apistan treatment. Thymol treatments did not provide as consistent results as Apistan or formic acid. Coefficient variation ratios for percentage mortality for the thymol group (CVT) with the Apistan and formic acid groups were CVT/CVA = 4.47 and CVT/CVFA = 6.76, respectively. In a second experiment, colonies received a 4-wk fall treatment of either 300 ml of 65% formic acid (n = 24) or four, 10% strips of Apistan (n = 6). The next spring, mite levels in the formic acid group (554.3 +/- 150.20 mites) were similar to those in the Apistan treatment group (571.3 +/- 145.05 mites) (P = 0.93). Additionally, the quantities of bees, brood, pollen, and nectar/honey in the two treatment groups were not significantly different (P > or = 0.50 each variable). These results suggest that formic acid is an effective alternative to Apistan as a fall treatment for varroa mites in temperate climates. PMID:10985013

  4. Graphene decorated with PtAu alloy nanoparticles: facile synthesis and promising application for formic acid oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Liao, Honggang; Liu, Jun; Aksay, Ilhan A.; Yin, Geping; Lin, Yuehe

    2011-03-01

    PtAu alloy nanoparticles (~ 3.2 nm in diameter) are synthesized in poly(diallyldimethylammonium chloride) (PDDA) aqueous solution and uniformly dispersed on graphene nanosheets. PtAu/graphene exhibits high electrocatalytic activity and stability for formic acid oxidation, which is attributed to the high dispersion of PtAu nanoparticles and the specific interaction between PtAu and graphene, indicating a promising catalyst for direct formic acid fuel cells. The facile method can be readily extended to the synthesis of other alloy nanoparticles.

  5. Hydrolysis of organosolv wheat pulp in formic acid at high temperature for glucose production.

    PubMed

    Kupiainen, Laura; Ahola, Juha; Tanskanen, Juha

    2012-07-01

    Organosolv methods can be used to delignify lignocellulosic crop residues for pulp production or to pretreat them prior to enzymatic hydrolysis for bioethanol production. In this study, organic solvent was used as an acidic hydrolysis catalyst to produce glucose. Hydrolysis experiments were carried out in 5-20% formic acid at 180-220 °C. Wheat straw pulp delignified with a formicodeli™ method was used as a raw material. It was found that glucose yields from pulp are significantly higher than yields from microcrystalline cellulose, a model component for cellulose hydrolysis. The results indicate that cellulose hydrolysis of real fibers takes place more selectively to glucose than hydrolysis of microcrystalline cellulose particles does. The effect of the particle size on pulp hydrolysis was investigated, the crystallinity of hydrolyzed pulp was measured by XRD analysis, and the product distribution and its influence on the process was discussed. PMID:22609651

  6. Photoluminescence and quantum yields of organic/inorganic hybrids prepared through formic acid solvolysis

    NASA Astrophysics Data System (ADS)

    Fu, Lianshe; Sá Ferreira, R. A.; Fernandes, M.; Nunes, S. C.; de Zea Bermudez, V.; Hungerford, Graham; Rocha, J.; Carlos, L. D.

    2008-03-01

    Three undoped di-urea cross-linked poly(oxyethylene) (POE)/siloxane hybrid matrices, classed as di-ureasils, incorporating POE segments with different lengths were prepared through the carboxylic acid solvolysis sol-gel method using formic acid. The resulting hybrids were characterized by X-ray diffraction, Fourier transform mid-infrared spectroscopy, 29Si and cross-polarization 13C magic-angle spinning nuclear magnetic resonance and photoluminescence spectroscopy. The hybrids' structure is essentially independent of the polymer chain length and the materials are room temperature white-light emitters with emission quantum yields of ˜10 ± 1% and lifetime average values between 2 and 4 ns. For the di-ureasil host with short polymer chains the solvolysis method favours the increase of the PL quantum yields relatively to conventional sol-gel route.

  7. An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

    NASA Technical Reports Server (NTRS)

    Keene, William C.; Talbot, Robert W.; Andreae, Meinrat O.; Beecher, Kristene; Berresheim, Harold

    1989-01-01

    During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH3COOH) were intercompared in central Virginia. HCOOH and CH3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH-impregnated quartz filters, K2CO3 and NaCO3-impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Performances of the mist chamber and K2CO3-impregnated filter techniques were evaluated using zero air and ambient air spiked with HCOOH(g) and CH3COOH(g), and formaldehyde from permeation sources. The advantages and drawbacks of these methods are reported and discussed.

  8. Mechanistic study of electrocatalytic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared absorption spectroscopy.

    PubMed

    Samjeské, Gabor; Miki, Atsushi; Ye, Shen; Osawa, Masatoshi

    2006-08-24

    Surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with cyclic voltammetry or chronoamperometry has been utilized to examine kinetic and mechanistic aspects of the electrocatalytic oxidation of formic acid on a polycrystalline Pt surface at the molecular scale. Formate is adsorbed on the electrode in a bridge configuration in parallel to the adsorption of linear and bridge CO produced by dehydration of formic acid. A solution-exchange experiment using isotope-labeled formic acids (H(12)COOH and H(13)COOH) reveals that formic acid is oxidized to CO(2) via adsorbed formate and the decomposition (oxidation) of formate to CO(2) is the rate-determining step of the reaction. The adsorption/oxidation of CO and the oxidation/reduction of the electrode surface strongly affect the formic acid oxidation by blocking active sites for formate adsorption and also by retarding the decomposition of adsorbed formate. The interplay of the involved processes also affects the kinetics and complicates the cyclic voltammograms of formic acid oxidation. The complex voltammetric behavior is comprehensively explained at the molecular scale by taking all these effects into account. PMID:16913790

  9. Excess Electron Attachment Induces Barrier-Free Proton Transfer in Anionic Complexes of Thymine and Uracil with Formic Acid

    SciTech Connect

    Haranczyk, Maciej; Dabkowska, Iwona; Rak, Janusz; Gutowski, Maciej S.; Nilles, J.M.; Stokes, Sarah; Radisic, Dunja; Bowen, Kit H.

    2004-06-03

    The anionic complexes of formic acid with uracil and thymine reveal broad features in photoelectron spectroscopy (PES) experiments with maxima at 1.7 and 1.1 eV, respectively. The results of quantum chemical calculations suggest that electron vertical detachment energies (VDE) of 1.6-1.9 eV correspond to anionic structures in which a proton has been transferred from the carboxylic group of the formic acid to the O8 atom of uracil or thymine. Smaller values of VDE (0.8 to 1.3 eV) correspond to chemically untransformed complexes, in which anionic uracil or thymine interacts through two hydrogen bonds with the carboxylic group of the intact formic acid. The recorded spectra and the results of quantum chemical calculations suggest that both nucleic acid bases undergo barrier-free proton transfer in anionic complexes with formic acid. The difference in experimental spectra of UF- and TF- provides an indication that the methyl group of thymine could make a difference in the intermolecular proton transfer.

  10. Production of hybrid diesel fuel precursors from carbohydrates and petrochemicals using formic acid as a reactive solvent.

    PubMed

    Zhou, Xiaoyuan; Rauchfuss, Thomas B

    2013-02-01

    We report the one-pot alkylation of mesitylene with carbohydrate-derived 5-(hydroxymethyl)furfural (HMF) as a step toward diesel-range liquids. Using FeCl(3) as a catalyst, HMF is shown to alkylate toluene, xylene, and mesitylene in high yields in CH(2)Cl(2) and MeNO(2) solvents. Efforts to extend this reaction to greener or safer solvents showed that most ether-based solvents are unsatisfactory. Acid catalysts (e.g, p-TsOH) also proved to be ineffective. Using formic acid as a reactive solvent, mesitylene could be alkylated to give mesitylmethylfurfural (MMF) starting from fructose with yields up to approximately 70 %. The reaction of fructose with formic acid in the absence of mesitylene gave rise to low yields of the formate ester of HMF, which indicates the stabilizing effect of replacing the hydroxyl substituent with mesityl. The arene also serves as a second phase into which the product is extracted. Even by using formic acid, the mesitylation of less expensive precursors such as glucose and cellulose proceeded only in modest yields (ca. 20 %). These simpler substrates were found to undergo mesitylation by using hydrogen chloride/formic acid via the intermediate chloromethylfurfural. PMID:23281330

  11. Determination of water-soluble forms of oxalic and formic acids in soils by ion chromatography

    NASA Astrophysics Data System (ADS)

    Karicheva, E.; Guseva, N.; Kambalina, M.

    2016-03-01

    Carboxylic acids (CA) play an important role in the chemical composition origin of soils and migration of elements. The content of these acids and their salts is one of the important characteristics for agrochemical, ecological, ameliorative and hygienic assessment of soils. The aim of the article is to determine water-soluble forms of same carboxylic acids — (oxalic and formic acids) in soils by ion chromatography with gradient elution. For the separation and determination of water-soluble carboxylic acids we used reagent-free gradient elution ion-exchange chromatography ICS-2000 (Dionex, USA), the model solutions of oxalate and formate ions, and leachates from soils of the Kola Peninsula. The optimal gradient program was established for separation and detection of oxalate and formate ions in water solutions by ion chromatography. A stability indicating method was developed for the simultaneous determination of water-soluble organic acids in soils. The method has shown high detection limits such as 0.03 mg/L for oxalate ion and 0.02 mg/L for formate ion. High signal reproducibility was achieved in wide range of intensities which correspond to the following ion concentrations: from 0.04 mg/g to 10 mg/L (formate), from 0.1 mg/g to 25 mg/L (oxalate). The concentration of formate and oxalate ions in soil samples is from 0.04 to 0.9 mg/L and 0.45 to 17 mg/L respectively.

  12. An ab initio study of some structural features and the rotational barriers in performic acid, formic acid and hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Bock, Charles W.; George, Philip; Trachtman, Mendel

    1981-02-01

    Calculations on performic acid at the 4-31G level, with and without bond functions with complete geometry optimization, and at the (9, 5) level, with and without polarization functions and rigid rotation, all give no sign of a well in the potential energy curve for rotation about the O/O bond axis in the region of 50° - 90° ; and all but the unaugmented 4-31G basis set find the cis- cis planar conformer to be the most stable form. Calculations at the (9,5) level with rigid rotation find the energies of the other planar conformers, relative to the cis- cis conformer, to be 0.94, 1.50 and 14.80 kcal mol -1 for the trans- trans, cis- trans and trans- cis structures respectively. These energies and also that for the barrier separating the cis- cis and cis- trans conformers, 1-2 kcal mol -1, are discussed in relation to corresponding data for formic acid, hydrogen peroxide and several planar four heavy-atom molecules. Dipole moment calculations using the same basis sets would seem to favor a skew conformation as the most stable for performic acid, but comparisons between calculated and experimental values for formic acid and for hydrogen peroxide cast doubt on the validity of such results.

  13. Structural Collapse of the Hydroquinone-Formic Acid Clathrate: A Pressure-Medium-Dependent Phase Transition.

    PubMed

    Eikeland, Espen; Thomsen, Maja K; Madsen, Solveig R; Overgaard, Jacob; Spackman, Mark A; Iversen, Bo B

    2016-03-14

    The energy landscape governing a new pressure-induced phase transition in the hydroquinone-formic acid clathrate is reported in which the host structure collapses, opening up the cavity channels within which the guest molecules migrate and order. The reversible isosymmetric phase transition causes significant changes in the morphology and the birefringence of the crystal. The subtle intermolecular interaction energies in the clathrate are quantified at varying pressures using novel model energies and energy frameworks. These calculations show that the high-pressure phase forms a more stable host network at the expense of less-stable host-guest interactions. The phase transition can be kinetically hindered using a nonhydrostatic pressure-transmitting medium, enabling the comparison of intermolecular energies in two polymorphic structures in the same pressure range. Overall this study illustrates a need for accurate intermolecular energies when analyzing self-assembly structures and supramolecular aggregates. PMID:26879515

  14. Degradation of trichloroethylene by hydrodechlorination using formic acid as hydrogen source over supported Pd catalysts.

    PubMed

    Yu, Xin; Wu, Ting; Yang, Xue-Jing; Xu, Jing; Auzam, Jordan; Semiat, Raphael; Han, Yi-Fan

    2016-03-15

    An advanced method for the degradation of trichloroethylene (TCE) over Pd/MCM-41 catalysts through a hydrogen-transfer was investigated. Formic acid (FA) was used instead of gaseous H2 as the hydrogen resource. As a model H-carrier compound, FA has proven to yield less by-products and second-hand pollution during the reaction. Several factors have been studied, including: the property of catalyst supports, Pd loading and size, temperature, initial concentrations of FA and TCE (potential impact on the reaction rates of TCE degradation), and FA decomposition. The intrinsic kinetics for TCE degradation were measured, while the apparent activation energies and the reaction orders with respect to TCE and FA were calculated through power law models. On the basis of kinetics, we assumed a plausible reaction pathway for TCE degradation in which the catalytic degradation of TCE is most likely the rate-determining step for this reaction. PMID:26685065

  15. Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile.

    PubMed

    Yu, Lei; Zhang, Qi; Li, Shu-Shuang; Huang, Jun; Liu, Yong-Mei; He, He-Yong; Cao, Yong

    2015-09-21

    Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. PMID:26224033

  16. Synthesis of highly dispersed and active palladium/carbon nanofiber catalyst for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Qin, Yuan-Hang; Yue-Jiang; Yang, Hou-Hua; Zhang, Xin-Sheng; Zhou, Xing-Gui; Niu, Li; Yuan, Wei-Kang

    2011-05-01

    Highly dispersed and active palladium/carbon nanofiber (Pd/CNF) catalyst is synthesized by NaBH4 reduction with trisodium citrate as the stabilizing agent. The obtained Pd/CNF catalyst is characterized by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The results show that the Pd nanoparticles with an average particle size of ca. 3.8 nm are highly dispersed on the CNF support even with a small ratio of citrate to Pd precursor, which is believed to be due to the pH adjustment of citrate stabilized colloidal Pd nanoparticles. The cyclic voltammetry and chronoamperometry techniques show that the obtained Pd/CNF catalyst exhibits good catalytic activity and stability for the electrooxidation of formic acid.

  17. Shape-dependent electrocatalysis: methanol and formic acid electrooxidation on preferentially oriented Pt nanoparticles.

    PubMed

    Solla-Gullón, J; Vidal-Iglesias, F J; López-Cudero, A; Garnier, E; Feliu, J M; Aldaz, A

    2008-07-01

    Reactivity towards methanol and formic acid electrooxidation on Pt nanoparticles with well characterised surfaces were studied and compared with the behaviour of single crystal electrodes with basal orientations. Polyoriented and preferential (100), (111) and (100)-(111) Pt nanoparticles were synthesised, cleaned preserving its surface structure, characterised and employed to evaluate the influence of the surface structure/shape of the Pt nanoparticles on these two relevant electrochemical reactions. The results pointed out that, in agreement with fundamental studies with Pt single crystal electrodes, the surface structure of the electrodes plays an important role on the reactivity of both oxidation processes, and thus the electrocatalytic properties strongly depend on the surface structure/shape of the nanoparticles, in particular on the presence of sites with (111) symmetry. These findings open the possibility of designing new and better electrocatalytic materials using decorated shape-controlled Pt nanoparticles as previously described with Pt single crystal electrodes. PMID:18563230

  18. Hydrogen generation during treatment of simulated high-level radioactive waste with formic acid

    SciTech Connect

    Ritter, J.A.; Zamecnik, J.R.; Hsu, C.W.

    1992-01-01

    The Integrated Defense Waste Processing Facility (DWPF) Melter System (IDMS), operated by the Savannah River Laboratory, is a one-fifth scale pilot facility used in support of the start-up and operation of the Department of Energy's DWPF. Five IDMS runs determined the effect of the presence of noble metals in HLW sludge on the H{sub 2} generation rate during the preparation of melter feed with formic acid. Overall, the results clearly showed that H{sub 2} generation in the DWPF SRAT could, at times, exceed the lower flammable limit of H{sub 2} in air (4 vol%), depending on such factors as offgas generation and air inleakage of the DWPF vessels. Therefore, the installation of a forced air purge system and H{sub 2} monitors were recommended to the DWPF to control the generation of H{sub 2} during melter feed preparation by fuel dilution.

  19. Hydrogen generation during treatment of simulated high-level radioactive waste with formic acid

    SciTech Connect

    Ritter, J.A.; Zamecnik, J.R.; Hsu, C.W.

    1992-05-01

    The Integrated Defense Waste Processing Facility (DWPF) Melter System (IDMS), operated by the Savannah River Laboratory, is a one-fifth scale pilot facility used in support of the start-up and operation of the Department of Energy`s DWPF. Five IDMS runs determined the effect of the presence of noble metals in HLW sludge on the H{sub 2} generation rate during the preparation of melter feed with formic acid. Overall, the results clearly showed that H{sub 2} generation in the DWPF SRAT could, at times, exceed the lower flammable limit of H{sub 2} in air (4 vol%), depending on such factors as offgas generation and air inleakage of the DWPF vessels. Therefore, the installation of a forced air purge system and H{sub 2} monitors were recommended to the DWPF to control the generation of H{sub 2} during melter feed preparation by fuel dilution.

  20. Cellulose nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated oxidation.

    PubMed

    Li, Bin; Xu, Wenyang; Kronlund, Dennis; Määttänen, Anni; Liu, Jun; Smått, Jan-Henrik; Peltonen, Jouko; Willför, Stefan; Mu, Xindong; Xu, Chunlin

    2015-11-20

    Cellulose nanocrystals (CNCs) as a renewable and biodegradable nanomaterial have wide application value. In this work, CNCs were extracted from bleached chemical pulp using two stages of isolation (i.e. formic acid (FA) hydrolysis and 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) mediated oxidation) under mild conditions. In the first stage, FA was used to remove hemicellulose, swell cellulose fibers, and release CNCs. The FA could be readily recovered and reused. In the second stage, the CNCs isolated by FA were further modified by TEMPO-mediated oxidation to increase the surface charge of CNCs. It was found that the modified CNCs with more ordered crystal structure and higher surface charge had better redispersibility and higher viscosity in aqueous phase. Therefore, the modified CNCs could be more effective when used as rheology modifier in the fields of water based coating, paint, food etc. PMID:26344319

  1. Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study

    SciTech Connect

    Durand, Jason; Senanayake, Sanjaya D; Mullins, David R; Suib, Steven

    2010-01-01

    The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.

  2. Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study

    SciTech Connect

    J Durand; S Senanayake; S Suib; D Mullins

    2011-12-31

    The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.

  3. Infrared and density functional theory studies of formic acid hydrate clusters in noble gas matrices

    NASA Astrophysics Data System (ADS)

    Ito, Fumiyuki

    2016-08-01

    Infrared absorption spectra of formic acid hydrate clusters (HCOOH)m(H2O)n have been measured in noble gas matrices (Ar and Kr). The concentration dependence of the spectra and the comparison with a previous experimental study on HCOOH(H2O) and HCOOH(H2O)2 [Geoge et al., Spectrochim. Acta, Part A 60 (2004) 3225] led to the identification of large clusters. Density functional theory calculations at the B3LYP-DCP/6-31+G(2d,2p) level were carried out to determine the anharmonic vibrational properties of the clusters, enabling a consistent assignment of the observed vibrational peaks to specific clusters.

  4. Energetics of methanol and formic acid oxidation on Pt(111): Mechanistic insights from adsorption calorimetry

    NASA Astrophysics Data System (ADS)

    Silbaugh, Trent L.; Karp, Eric M.; Campbell, Charles T.

    2016-08-01

    The catalytic and electrocatalytic oxidation and reforming of methanol and formic acid have received intense interest due to potential use in direct fuel cells and as prototype models for understanding electrocatalysis. Consequently, the reaction energy diagram (energies of all the adsorbed intermediates and activation energies of all the elementary steps) have been estimated for these reactions on Pt(111) by density functional theory (DFT) in several studies. However, no experimental measurement of these energy diagrams have been reported, nor is there a consensus on the mechanisms. Here, we use energies of key intermediates on Pt(111) from single crystal adsorption calorimetry (SCAC) and temperature programmed desorption (TPD) to build a combined energy diagram for these reactions. It suggests a new pathway involving monodentate formate as a key intermediate, with bidentate formate only being a spectator species that slows the rate. This helps reconcile conflicting proposed mechanisms.

  5. A Large Underestimate of Formic Acid from Tropical Fires: Constraints from Space-Borne Measurements.

    PubMed

    Chaliyakunnel, S; Millet, D B; Wells, K C; Cady-Pereira, K E; Shephard, M W

    2016-06-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids and a dominant source of atmospheric acidity. Recent work indicates a major gap in the HCOOH budget, with atmospheric concentrations much larger than expected from known sources. Here, we employ recent space-based observations from the Tropospheric Emission Spectrometer with the GEOS-Chem atmospheric model to better quantify the HCOOH source from biomass burning, and assess whether fire emissions can help close the large budget gap for this species. The space-based data reveal a severe model HCOOH underestimate most prominent over tropical burning regions, suggesting a major missing source of organic acids from fires. We develop an approach for inferring the fractional fire contribution to ambient HCOOH and find, based on measurements over Africa, that pyrogenic HCOOH:CO enhancement ratios are much higher than expected from direct emissions alone, revealing substantial secondary organic acid production in fire plumes. Current models strongly underestimate (by 10 ± 5 times) the total primary and secondary HCOOH source from African fires. If a 10-fold bias were to extend to fires in other regions, biomass burning could produce 14 Tg/a of HCOOH in the tropics or 16 Tg/a worldwide. However, even such an increase would only represent 15-20% of the total required HCOOH source, implying the existence of other larger missing sources. PMID:27149080

  6. Highly Active Pt(3)Pb and Core-Shell Pt(3)Pb-Pt Electrocatalysts for Formic Acid Oxidation

    SciTech Connect

    Kang Y.; Stach E.; Qi L.; Li M.; Diaz R.E.; Su D.; Adzic R.R.; Li J.; Murray C.B.

    2012-03-27

    Formic acid is a promising chemical fuel for fuel cell applications. However, due to the dominance of the indirect reaction pathway and strong poisoning effects, the development of direct formic acid fuel cells has been impeded by the low activity of existing electrocatalysts at desirable operating voltage. We report the first synthesis of Pt{sub 3}Pb nanocrystals through solution phase synthesis and show they are highly efficient formic acid oxidation electrocatalysts. The activity can be further improved by manipulating the Pt{sub 3}Pb-Pt core-shell structure. Combined experimental and theoretical studies suggest that the high activity from Pt{sub 3}Pb and the Pt-Pb core-shell nanocrystals results from the elimination of CO poisoning and decreased barriers for the dehydrogenation steps. Therefore, the Pt{sub 3}Pb and Pt-Pb core-shell nanocrystals can improve the performance of direct formic acid fuel cells at desired operating voltage to enable their practical application.

  7. Hydrogenation of CO2 to Formic Acid with a Highly Active Ruthenium Acriphos Complex in DMSO and DMSO/Water.

    PubMed

    Rohmann, Kai; Kothe, Jens; Haenel, Matthias W; Englert, Ulli; Hölscher, Markus; Leitner, Walter

    2016-07-25

    The novel [Ru(Acriphos)(PPh3 )(Cl)(PhCO2 )] [1; Acriphos=4,5-bis(diphenylphosphino)acridine] is an excellent precatalyst for the hydrogenation of CO2 to give formic acid in dimethyl sulfoxide (DMSO) and DMSO/H2 O without the need for amine bases as co-reagents. Turnover numbers (TONs) of up to 4200 and turnover frequencies (TOFs) of up to 260 h(-1) were achieved, thus rendering 1 one of the most active catalysts for CO2 hydrogenations under additive-free conditions reported to date. The thermodynamic stabilization of the reaction product by the reaction medium, through hydrogen bonds between formic acid and clusters of solvent or water, were rationalized by DFT calculations. The relatively low final concentration of formic acid obtained experimentally under catalytic conditions (0.33 mol L(-1) ) was shown to be limited by product-dependent catalyst inhibition rather than thermodynamic limits, and could be overcome by addition of small amounts of acetate buffer, thus leading to a maximum concentration of free formic acid of 1.27 mol L(-1) , which corresponds to optimized values of TON=16×10(3) and TOFavg ≈10(3)  h(-1) . PMID:27356513

  8. Formic and Acetic Acids in Degradation Products of Plant Volatiles Elicit Olfactory and Behavioral Responses from an Insect Vector.

    PubMed

    George, Justin; Robbins, Paul S; Alessandro, Rocco T; Stelinski, Lukasz L; Lapointe, Stephen L

    2016-05-01

    Volatile phytochemicals play a role in orientation by phytophagous insects. We studied antennal and behavioral responses of the Asian citrus psyllid, Diaphorina citri, vector of the citrus greening disease pathogen. Little or no response to citrus leaf volatiles was detected by electroantennography. Glass cartridges prepared with β-ocimene or citral produced no response initially but became stimulatory after several days. Both compounds degraded completely in air to a number of smaller molecules. Two peaks elicited large antennal responses and were identified as acetic and formic acids. Probing by D. citri of a wax substrate containing odorants was significantly increased by a blend of formic and acetic acids compared with either compound separately or blends containing β-ocimene and/or citral. Response surface modeling based on a 4-component mixture design and a 2-component mixture-amount design predicted an optimal probing response on wax substrate containing a blend of formic and acetic acids. Our study suggests that formic and acetic acids play a role in host selection by D. citri and perhaps by phytophagous insects in general even when parent compounds from which they are derived are not active. These results have implications for the investigation of arthropod olfaction and may lead to elaboration of attract-and-kill formulations to reduce nontarget effects of chemical control in agriculture. PMID:26857741

  9. Enhanced catalytic performance of carbon supported palladium nanoparticles by in-situ synthesis for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Yao, Shikui; Li, Guoqiang; Liu, Changpeng; Xing, Wei

    2015-06-01

    The development of facile, surfactant-free strategy for the scale-up production of catalysts with superior performance for energy science is an interesting challenge. Pd/C is synthesized using an in-situ method from PdO/C for formic acid electrooxidation based on the reducibility of formic acid. The morphology, composition and electrocatalytic properties are investigated using transmission electronmicroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, linear scan voltammograms (LSV) and chronoamperometry. The in-situ synthesized Pd nanoparticles show better distribution and smaller average particle size than the normally synthesized Pd/C, which indicates that the well-known Ostwald ripening is most limited in the synthesis process. The electrochemical measurements show that the Pd/C catalyst exhibits enhanced performance towards formic acid electrooxidation. For example, the peak current of the Pd/C catalyst is approximately three times that of the homemade Pd/C catalyst and twice as high as that of the commercial Pd/C catalyst in the LSV test. The in-situ synthesized Pd/C catalyst has potential application for direct formic acid fuel cells, and the in-situ route should be an effective strategy to synthesize high performance catalysts.

  10. Enhanced formic acid oxidation on polycrystalline platinum modified by spontaneous deposition of gold. Fourier transform infrared spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Cappellari, Paula S.; García, Gonzalo; Florez-Montaño, Jonathan; Barbero, Cesar A.; Pastor, Elena; Planes, Gabriel A.

    2015-11-01

    Formic acid and adsorbed carbon monoxide electrooxidation on polycrystalline Pt and Au-modified Pt surfaces were studied by cyclic voltammetry, lineal sweep voltammetry and in-situ Fourier transform infrared spectroscopy techniques. With this purpose, a polycrystalline Pt electrode was modified by spontaneous deposition of gold atoms, achieving a gold surface coverage (θ) in the range of 0 ≤ θ ≤ 0.47. Results indicate the existence of two main pathways during the formic acid oxidation reaction, i.e. dehydration and dehydrogenation routes. At higher potentials than 0.5 V the dehydrogenation pathway appears to be the operative at both Pt and Au electrodes. Meanwhile, the dehydration reaction is the main pathway for Pt at lower potentials than 0.5 V. It was found that reaction routes are easily tuned by Au deposition on the Pt sites responsible for the formic acid dehydration reaction, and hence for the catalytic formation of adsorbed carbon monoxide. Gold deposition on these Pt open sites produces an enhanced activity toward the HCOOH oxidation reaction. In general terms, the surface inhibition of the reaction by adsorbed intermediates (indirect pathway) is almost absent at gold-modified Pt electrodes, and therefore the direct pathway appears as the main route during the formic acid electrooxidation reaction.

  11. Electrostatic Self-Assembly of Pt-around-Au Nanocomposite with High Activity towards Formic Acid Oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Yin, Geping; Lin, Yuehe

    2010-03-01

    Pt-around-Au nanocomposite is synthesized using the electrostatic selfassembly method. This catalyst shows significantly improved activity towards formic acid oxidation. The possible reason is the efficient spillover of HCOO from Au to the surrounding Pt NPs, where HCOO is further oxidized to CO2.

  12. Valence anions in complexes of adenine and 9-methyladenine with formic acid: stabilization by intermolecular proton transfer.

    PubMed

    Mazurkiewicz, Kamil; Harańczyk, Maciej; Gutowski, Maciej; Rak, Janusz; Radisic, Dunja; Eustis, Soren N; Wang, Di; Bowen, Kit H

    2007-02-01

    Photoelectron spectra of adenine-formic acid (AFA(-)) and 9-methyladenine-formic acid (MAFA(-)) anionic complexes have been recorded with 2.540 eV photons. These spectra reveal broad features with maxima at 1.5-1.4 eV that indicate formation of stable valence anions in the gas phase. The neutral and anionic complexes of adenine/9-methyladenine and formic acid were also studied computationally at the B3LYP, second-order Møller-Plesset, and coupled-cluster levels of theory with the 6-31++G** and aug-cc-pVDZ basis sets. The neutral complexes form cyclic hydrogen bonds, and the most stable dimers are bound by 17.7 and 16.0 kcal/mol for AFA and MAFA, respectively. The theoretical results indicate that the excess electron in both AFA(-) and MAFA(-) occupies a pi* orbital localized on adenine/9-methyladenine, and the adiabatic stability of the most stable anions amounts to 0.67 and 0.54 eV for AFA(-) and MAFA(-), respectively. The attachment of the excess electron to the complexes induces a barrier-free proton transfer (BFPT) from the carboxylic group of formic acid to a N atom of adenine or 9-methyladenine. As a result, the most stable structures of the anionic complexes can be characterized as neutral radicals of hydrogenated adenine (9-methyladenine) solvated by a deprotonated formic acid. The BFPT to the N atoms of adenine may be biologically relevant because some of these sites are not involved in the Watson-Crick pairing scheme and are easily accessible in the cellular environment. We suggest that valence anions of purines might be as important as those of pyrimidines in the process of DNA damage by low-energy electrons. PMID:17263404

  13. The Trimethylamine-Formic Acid Complex: Microwave Characterization of a Prototype for Potential Precursors to Atmospheric Aerosol.

    PubMed

    Mackenzie, Rebecca B; Dewberry, Christopher T; Leopold, Kenneth R

    2016-04-14

    The reactions of amines and carboxylic acids have recently received attention for their possible role in the formation of atmospheric aerosol. Here, we report a microwave study of the trimethylamine-formic acid hydrogen-bonded complex, a simple prototype in which to study amine-carboxylic acid interactions. Spectra of three isotopologues of the system have been observed using a tandem cavity and chirped-pulse Fourier transform microwave spectrometer. The complex has a plane of symmetry, with the acidic proton of the formic acid directed toward the lone pair of the nitrogen. The zero-point-averaged hydrogen bond length is 1.702 Å, and the O-H···N angle is 177°. (14)N nuclear quadrupole hyperfine structure has been used to assess the degree of proton transfer from the formic acid to the trimethylamine. Experimental results are supplemented with density functional theory calculations. M06-2X/6-311++G(3df,3pd) calculations indicate a binding energy of 16.8 kcal/mol with counterpoise correction (17.4 kcal/mol without counterpoise correction). PMID:27023479

  14. Catalytic Hydrotreatment of Humins in Mixtures of Formic Acid/2-Propanol with Supported Ruthenium Catalysts.

    PubMed

    Wang, Yuehu; Agarwal, Shilpa; Kloekhorst, Arjan; Heeres, Hero Jan

    2016-05-10

    The catalytic hydrotreatment of humins, which are the solid byproducts from the conversion of C6 sugars (glucose, fructose) into 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), by using supported ruthenium catalysts has been investigated. Reactions were carried out in a batch setup at elevated temperatures (400 °C) by using a hydrogen donor (formic acid (FA) in isopropanol (IPA) or hydrogen gas), with humins obtained from d-glucose. Humin conversions of up to 69 % were achieved with Ru/C and FA, whereas the performance for Ru on alumina was slightly poorer (59 % humin conversion). Humin oils were characterized by using a range of analytical techniques (GC, GC-MS, GCxGC, gel permeation chromatography) and were shown to consist of monomers, mainly alkyl phenolics (>45 % based on compounds detectable by GC) and higher oligomers. A reaction network for the reaction is proposed based on structural proposals for humins and the main reaction products. PMID:26836970

  15. Suppression of Growth Rate of Colony-Associated Fungi by High Fructose Corn Syrup Feeding Supplement, Formic Acid, and Oxalic Acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Select colony-associated fungi (bee isolates). Absidia sp., Ascosphaera apis, Aspergillus flavus, Fusarium sp., Penicillium glabrum, Mucor sp., showed a 40% reduction in radial growth rate with formic acid, a 28% reduction with oxalic acid, and a 15% reduction with fructose and high fructose corn sy...

  16. Electrocatalytic properties of carbon-supported Pt-Ru catalysts with the high alloying degree for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Chen, Yu; Zhou, Yiming; Tang, Yawen; Lu, Tianhong

    A series of carbon-supported bimetallic Pt-Ru catalysts with high alloying degree and different Pt/Ru atomic ratio have been prepared by a chemical reduction method in the H 2O/ethanol/tetrahydrofuran (THF) mixture solvent. The structural and electronic properties of catalysts are characterized using X-ray reflection (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM). The electrooxidation of formic acid on these Pt-Ru nanoparticles are investigated by using cyclic voltammetry, chronoamperometry and CO-stripping measurements. The results of electrochemical measurements illustrate that the alloying degree and Pt/Ru atomic ratio of Pt-Ru catalyst play an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for formic acid electrooxidation due to the bifunctional mechanism and the electronic effect. Since formic acid is an intermediate in the methanol electrooxidation on Pt electrode in acidic electrolyte, the observation provides an additional fundamental understanding of the structure-activity relationship of Pt-Ru catalyst for methanol electrooxidation.

  17. Formic acid electrooxidation on thallium-decorated shape-controlled platinum nanoparticles: an improvement in electrocatalytic activity.

    PubMed

    Busó-Rogero, Carlos; Perales-Rondón, Juan V; Farias, Manuel J S; Vidal-Iglesias, Francisco J; Solla-Gullon, Jose; Herrero, Enrique; Feliu, Juan M

    2014-07-21

    Thallium modified shape-controlled Pt nanoparticles were prepared and their electrocatalytic activity towards formic acid electrooxidation was evaluated in 0.5 M sulfuric acid. The electrochemical and in situ FTIR spectroscopic results show a remarkable improvement in the electrocatalytic activity, especially in the low potential region (around 0.1-0.2 V vs. RHE). Cubic Pt nanoparticles modified with Tl were found to be more active than the octahedral Pt ones in the entire range of Tl coverages and potential windows. In situ FTIR spectra indicate that the promotional effect produced by Tl results in the inhibition of the poisoning step leading to COads, thus improving the onset potential for the complete formic acid oxidation to CO2. Chronoamperometric experiments were also performed at 0.2 V to evaluate the stability of the electrocatalysts at constant potential. Finally, experiments with different concentrations of formic acid (0.05-1 M) were also carried out. In all cases, Tl-modified cubic Pt nanoparticles result to be the most active. All these facts reinforce the importance of controlling the surface structure of the electrocatalysts to optimize their electrocatalytic properties. PMID:24638124

  18. Radiation-induced transformations of matrix-isolated formic acid: evidence for the HCOOH → HOCO + H channel.

    PubMed

    Ryazantsev, Sergey V; Feldman, Vladimir I

    2015-11-11

    The effect of X-ray irradiation on the isolated formic acid molecules (HCOOH) in solid noble gas matrices (Xe, Kr, Ar, and Ne) at very low temperatures (6 K) was first studied by FTIR spectroscopy. Carbon oxides (CO and CO2) and hydrocarboxyl radicals (HOCO) have been detected as the principal degradation products. The formation of HOCO radicals represents a primary dissociation channel for formic acid, which was not reported previously under UV photolysis in solids. This reaction can be explained by the involvement of the recombination-induced excited states, which are not populated in photolysis. The effects of the matrix and the absorbed dose on the product formation were studied in detail and possible mechanisms are discussed with particular attention to the difference between radiolysis and UV-photolysis of the matrix-isolated formic acid. The results obtained provide a new insight into the effects of high-energy impact on the simplest carboxylic acid with possible implications to the astrochemical problems, in particular, the prebiotic evolution in the interstellar medium. PMID:26524429

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  20. Enhancement of biomass conversion in catalytic fast pyrolysis by microwave-assisted formic acid pretreatment.

    PubMed

    Feng, Yu; Li, Guangyu; Li, Xiangyu; Zhu, Ning; Xiao, Bo; Li, Jian; Wang, Yujue

    2016-08-01

    This study investigated microwave-assisted formic acid (MW-FA) pretreatment as a possible way to improve aromatic production from catalytic fast pyrolysis (CFP) of lignocellulosic biomass. Results showed that short duration of MW-FA pretreatment (5-10min) could effectively disrupt the recalcitrant structure of beech wood and selectively remove its hemicellulose and lignin components. This increased the accessibility of cellulose component of biomass to subsequent thermal conversion in CFP. Consequently, the MW-FA pretreated beech wood produced 14.0-28.3% higher yields (26.4-29.8C%) for valuable aromatic products in CFP than the untreated control (23.2C%). In addition, the yields of undesired solid residue (char/coke) decreased from 33.1C% for the untreated control to 28.6-29.8C% for the MW-FA pretreated samples. These results demonstrate that MW-FA pretreatment can provide an effective way to improve the product distribution from CFP of lignocellulose. PMID:27176672

  1. Fundamental mechanistic studies in formic acid decomposition on transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Mavrikakis, Manos

    2014-03-01

    Formic acid (HCOOH) is a simple molecule that is an abundant product of biomass processing and can serve as an internal source of hydrogen for oxygen removal and upgrading of biomass to chemicals and fuels. In addition, HCOOH can be used as a fuel for low temperature direct fuel cells. We present a systematic study of the HCOOH decomposition reaction mechanism starting from first-principles and including reactivity experiments and microkinetic modeling. In particular, periodic self-consistent Density Functional Theory (DFT) calculations are performed to determine the stability of reactive intermediates and activation energy barriers of elementary steps. Pre-exponential factors are determined from vibrational frequency calculations. Mean-field microkinetic models are developed and calculated reaction rates and reaction orders are then compared with experimentally measured ones. These comparisons provide useful insights on the nature of the active site, most-abundant surface intermediates as a function of reaction conditions and feed composition. Trends across metals on the fundamental atomic-scale level up to selectivity trends will be discussed. Finally, we identify from first-principles alloy surfaces, which may possess better catalytic properties for selective dehydrogenation of HCOOH than monometallic surfaces, thereby guiding synthesis towards promising novel catalytic materials. Work supported as part of the Institute of Atom-efficient Chemical Transformation (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  2. Air-breathing direct formic acid microfluidic fuel cell with an array of cylinder anodes

    NASA Astrophysics Data System (ADS)

    Zhu, Xun; Zhang, Biao; Ye, Ding-Ding; Li, Jun; Liao, Qiang

    2014-02-01

    An air-breathing direct formic acid membraneless microfluidic fuel cell using graphite cylinder arrays as the anode is proposed. The three dimensional anode volumetrically extends the reactive surface area and improves fuel utilization. The effects of spacer configuration, fuel and electrolyte concentration as well as reactant flow rate on the species transport and cell performance are investigated. The dynamic behavior of generated CO2 bubbles is visualized and its effect on current generation is discussed. The results show that the absence of two spacers adjacent to the cathode surface improves the cell performance by reducing the proton transfer resistance. The CO2 gas bubbles are constrained within the anode array and expelled by the fluid flow periodically. Proper reactant concentration and flow rate are crucial for cell operation. At optimum conditions, a maximum current density of 118.3 mA cm-3 and a peak power density of 21.5 mW cm-3 are obtained. In addition, benefit from the volumetrically stacked anodes and enhanced fuel transfer, the maximum single pass fuel utilization rate reaches up to 87.6% at the flow rate of 1 mL h-1.

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

    SciTech Connect

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

    2015-09-15

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

  4. Rheological Properties and Electrospinnability of High-Amylose Starch in Formic Acid.

    PubMed

    Lancuški, Anica; Vasilyev, Gleb; Putaux, Jean-Luc; Zussman, Eyal

    2015-08-10

    Starch derivatives, such as starch-esters, are commonly used as alternatives to pure starch due to their enhanced mechanical properties. However, simple and efficient processing routes are still being sought out. In the present article, we report on a straightforward method for electrospinning high-amylose starch-formate nanofibers from 17 wt % aqueous formic acid (FA) dispersions. The diameter of the electrospun starch-formate fibers ranged from 80 to 300 nm. The electrospinnability window between starch gelatinization and phase separation was determined using optical microscopy and rheological studies. This window was shown to strongly depend on the water content in the FA dispersions. While pure FA rapidly gelatinized starch, yielding solutions suitable for electrospinning within a few hours at room temperature, the presence of water (80 and 90 vol % FA) significantly delayed gelatinization and dissolution, which deteriorated fiber quality. A complete destabilization of the electrospinning process was observed in 70 vol % FA dispersions. Optical micrographs showed that FA induced a disruption of starch granule with a loss of crystallinity confirmed by X-ray diffraction. As a result, starch fiber mats exhibited a higher elongation at break when compared to brittle starch films. PMID:26192477

  5. Shape-dependent electrocatalysis: formic acid electrooxidation on cubic Pd nanoparticles.

    PubMed

    Vidal-Iglesias, Francisco J; Arán-Ais, Rosa M; Solla-Gullón, José; Garnier, Emmanuel; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2012-08-01

    The electrocatalytic properties of palladium nanocubes towards the electrochemical oxidation of formic acid were studied in H(2)SO(4) and HClO(4) solutions and compared with those of spherical Pd nanoparticles. The spherical and cubic Pd nanoparticles were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The intrinsic electrocatalytic properties of both nanoparticles were shown to be strongly dependent on the amount of metal deposited on the gold substrate. Thus, to properly compare the activity of both systems (spheres and nanocubes), the amount of sample has to be optimized to avoid problems due to a lower diffusion flux of reactants in the internal parts of the catalyst layer resulting in a lower apparent activity. Under the optimized conditions, the activity of the spheres and nanocubes was very similar between 0.1 and 0.35 V. From this potential value, the activity of the Pd nanocubes was remarkably higher. This enhanced electrocatalytic activity was attributed to the prevalence of Pd(100) facets in agreement with previous studies with Pd single crystal electrodes. The effect of HSO(4)(-)/SO(4)(2-) desorption-adsorption was also evaluated. The activity found in HClO(4) was significantly higher than that obtained in H(2)SO(4) in the whole potential range. PMID:22722609

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

    DOE PAGESBeta

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

    2015-09-15

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

  7. Enhanced formic acid electro-oxidation reaction on ternary Pd-Ir-Cu/C catalyst

    NASA Astrophysics Data System (ADS)

    Chen, Jinwei; Zhang, Jie; Jiang, Yiwu; Yang, Liu; Zhong, Jing; Wang, Gang; Wang, Ruilin

    2015-12-01

    Aim to further reduce the cost of Pd-Ir for formic acid electro-oxidation (FAEO), the Cu was used to construct a ternary metallic alloy catalyst. The prepared catalysts are characterized using XRD, TGA, EDX, TEM, XPS, CO-stripping, cyclic voltammetry and chronoamperometry. It is found that the Pd18Ir1Cu6 nanoparticles with a mean size of 3.3 nm are highly dispersed on carbon support. Componential distributions on catalyst are consistent with initial contents. Electrochemical measurements show that the PdIrCu/C catalyst exhibits the highest activity for FAEO. The mass activity of Pd in Pd18Ir1Cu6/C at 0.16 V (vs. SCE) is about 1.47, 1.62 and 2.08 times as high as that of Pd18Cu6/C, Pd18Ir1/C and Pd/C, respectively. The activity enhancement of PdIrCu/C should be attributed to the weakened CO adsorption strength and the removal of adsorbed intermediates at lower potential with the addition of Cu and Ir.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  9. Revisiting formic acid decomposition on metallic powder catalysts: Exploding the HCOOH decomposition volcano curve

    NASA Astrophysics Data System (ADS)

    Tang, Yadan; Roberts, Charles A.; Perkins, Ryan T.; Wachs, Israel E.

    2016-08-01

    This study revisits the classic volcano curve for HCOOH decomposition by metal catalysts by taking a modern catalysis approach. The metal catalysts (Au, Ag, Cu, Pt, Pd, Ni, Rh, Co and Fe) were prepared by H2 reduction of the corresponding metal oxides. The number of surface active sites (Ns) was determined by formic acid chemisorption. In situ IR indicated that both monodentate and bidentate/bridged surface HCOO* were present on the metals. Heats of adsorption (ΔHads) for surface HCOO* values on metals were taken from recently reported DFT calculations. Kinetics for surface HCOO* decomposition (krds) were determined with TPD spectroscopy. Steady-state specific activity (TOF = activity/Ns) for HCOOH decomposition over the metals was calculated from steady-state activity (μmol/g-s) and Ns (μmol/g). Steady-state TOFs for HCOOH decomposition weakly correlated with surface HCOO* decomposition kinetics (krds) and ΔHads of surface HCOO* intermediates. The plot of TOF vs. ΔHads for HCOOH decomposition on metal catalysts does not reproduce the classic volcano curve, but shows that TOF depends on both ΔHads and decomposition kinetics (krds) of surface HCOO* intermediates. This is the first time that the classic catalysis study of HCOOH decomposition on metallic powder catalysts has been repeated since its original publication.

  10. Tunneling splittings in formic acid dimer: An adiabatic approximation to the Herring formula

    NASA Astrophysics Data System (ADS)

    Jain, Amber; Sibert, Edwin L.

    2015-02-01

    Small symmetric molecules and low-dimensional model Hamiltonians are excellent systems for benchmarking theories to compute tunneling splittings. In this work, we investigate a three dimensional model Hamiltonian coupled to a harmonic bath that describes concerted proton transfer in the formic acid dimer. The three modes include the symmetric proton stretch, the symmetric dimer rock, and the dimer stretch. These modes provide a paradigm for the symmetric and anti-symmetric coupled tunneling pathways, these being recognized in the literature as two of the more important classes of coupling. The effects of selective vibrational excitation and coupling to a bath on the tunneling splittings are presented. The splittings for highly excited states are computed using a novel method that makes an adiabatic approximation to the Herring estimate. Results, which are in excellent agreement with the exact splittings, are compared with those obtained using the Makri-Miller approach. This latter method has been shown to provide quality results for tunneling splittings including highly excited vibrational states.

  11. Tunneling splittings in formic acid dimer: An adiabatic approximation to the Herring formula

    SciTech Connect

    Jain, Amber; Sibert, Edwin L.

    2015-02-28

    Small symmetric molecules and low-dimensional model Hamiltonians are excellent systems for benchmarking theories to compute tunneling splittings. In this work, we investigate a three dimensional model Hamiltonian coupled to a harmonic bath that describes concerted proton transfer in the formic acid dimer. The three modes include the symmetric proton stretch, the symmetric dimer rock, and the dimer stretch. These modes provide a paradigm for the symmetric and anti-symmetric coupled tunneling pathways, these being recognized in the literature as two of the more important classes of coupling. The effects of selective vibrational excitation and coupling to a bath on the tunneling splittings are presented. The splittings for highly excited states are computed using a novel method that makes an adiabatic approximation to the Herring estimate. Results, which are in excellent agreement with the exact splittings, are compared with those obtained using the Makri-Miller approach. This latter method has been shown to provide quality results for tunneling splittings including highly excited vibrational states.

  12. Microwave measurements of the tropolone-formic acid doubly hydrogen bonded dimer.

    PubMed

    Pejlovas, Aaron M; Serrato, Agapito; Lin, Wei; Kukolich, Stephen G

    2016-01-28

    The microwave spectrum was measured for the doubly hydrogen bonded dimer formed between tropolone and formic acid. The predicted symmetry of this dimer was C2v(M), and it was expected that the concerted proton tunneling motion would be observed. After measuring 25 a- and b-type rotational transitions, no splittings which could be associated with a concerted double proton tunneling motion were observed. The calculated barrier to the proton tunneling motion is near 15,000 cm(-1), which would likely make the tunneling frequencies too small to observe in the microwave spectra. The rotational and centrifugal distortion constants determined from the measured transitions were A = 2180.7186(98) MHz, B = 470.873 90(25) MHz, C = 387.689 84(22) MHz, DJ = 0.0100(14) kHz, DJK = 0.102(28) kHz, and DK = 13.2(81) kHz. The B3LYP/aug-cc-pVTZ calculated rotational constants were within 1% of the experimentally determined values. PMID:26827216

  13. Phase properties of carbon-supported platinum-gold nanoparticles for formic acid eletro-oxidation

    NASA Astrophysics Data System (ADS)

    Liao, Mengyin; Xiong, Jihai; Fan, Min; Shi, Jinming; Luo, Chenglong; Zhong, Chuan-Jian; Chen, Bing H.

    2015-10-01

    The design of active and robust bimetallic nanocatalysts requires the control of the nanoscale alloying, phase-segregation and the correlation between nanoscale phase-segregation and catalytic properties. To enhance the performance and durability of formic acid oxidation reaction in fuel-cell applications, we prepared a platinum-gold (PtAu) nanocatalyst with controlled morphology and composition. The catalyst is further treated by calcination under controlled temperature and atmosphere. The morphology of the bimetallic nanoparticles is determined by transmission electron microscopy. The nanoscale phase properties and surface composition are carried out by X-ray diffraction and X-ray photoelectron spectroscopy. Cyclic voltammetry measurements demonstrated that the catalytic activity is highly dependent on the nanoscale evolution of alloying and phase segregation. The mass activity of as-prepared Pt50Au50/C with 600 °C treatment temperature is about 11 times higher than that of commercial Pt/C. Stability tests showed no obvious loss of activity after 500 potential cycles. The high activity and stability are attributed to lattice contraction effect as a result of the high thermal treatment condition. Our findings demonstrate the importance of phase segregation at the nanoscale in harnessing the true electrocatalytic potential of bimetallic nanoparticles.

  14. Microwave measurements of the tropolone-formic acid doubly hydrogen bonded dimer

    NASA Astrophysics Data System (ADS)

    Pejlovas, Aaron M.; Serrato, Agapito; Lin, Wei; Kukolich, Stephen G.

    2016-01-01

    The microwave spectrum was measured for the doubly hydrogen bonded dimer formed between tropolone and formic acid. The predicted symmetry of this dimer was C2v(M), and it was expected that the concerted proton tunneling motion would be observed. After measuring 25 a- and b-type rotational transitions, no splittings which could be associated with a concerted double proton tunneling motion were observed. The calculated barrier to the proton tunneling motion is near 15 000 cm-1, which would likely make the tunneling frequencies too small to observe in the microwave spectra. The rotational and centrifugal distortion constants determined from the measured transitions were A = 2180.7186(98) MHz, B = 470.873 90(25) MHz, C = 387.689 84(22) MHz, DJ = 0.0100(14) kHz, DJK = 0.102(28) kHz, and DK = 13.2(81) kHz. The B3LYP/aug-cc-pVTZ calculated rotational constants were within 1% of the experimentally determined values.

  15. Formic acid oxidation on antimony-covered platinum films with a preferential (100) orientation

    NASA Astrophysics Data System (ADS)

    Bertin, Erwan; Garbarino, Sébastien; Guay, Daniel

    2015-12-01

    The spontaneous adsorption of Sb onto nanostructured platinum electrodeposited films with a preferential (100) surface orientation, hereafter denoted Pt100 pref, was studied by means of electrochemical quartz microbalance (EQCM) and X-ray photoelectron spectroscopy. EQCM results indicated the formation of a Sb monolayer, while XPS analyses confirmed that a fraction of the as-adsorbed Sb adatoms were in a metallic state, while the others were in an oxidized state. After cycling, all of the Sb adatoms were in a metallic state. The electrocatalytic performances towards formic acid oxidation were assessed through cyclic voltammetry and chronoamperometry. On Pt100 pref, the presence of Sb markedly increased the current on the forward scan up to the potential value (typically 0.20 V) corresponding to a redox reaction occurring on the adatom. After one hour of electrolysis, the current on the Pt100 pref electrode covered with 75% Sb was ca. 15 mA cm-2geometric at 0.14 V vs SCE, which is 100 times higher than on the bare Pt100 pref electrode. The short- and long-term activities of the Pt100 pref electrode were maintained even when the electrode was disoriented through potential cycling in the Pt oxide formation and reduction region.

  16. Rotational spectra and gas phase structure of the maleimide - Formic acid doubly hydrogen bonded dimer

    NASA Astrophysics Data System (ADS)

    Pejlovas, Aaron M.; Kukolich, Stephen G.

    2016-03-01

    Rotational transitions were measured for the maleimide - formic acid doubly hydrogen bonded dimer using a Flygare-Balle type pulsed-beam Fourier transform microwave spectrometer. No splittings caused by possible concerted double proton tunneling motion were observed. Experimental rotational constants (MHz), quadrupole coupling constants (MHz), and centrifugal distortion constants (kHz) were determined for the parent and three deuterium substituted isotopologues. The values for the parent are A = 2415.0297(10), B = 784.37494(38), C = 592.44190(33), DJ = 0.0616(64), DJK = -0.118(35), DK = -1.38(15), 1.5χaa = 2.083(14), and 0.25(χbb-χcc) = 1.1565(29). The hydrogen bond lengths were determined using a nonlinear least squares structure fitting program. Rotational constants for this complex are consistent with a planar structure, with an inertial defect of Δ = -0.528 amu Å2. The B3LYP calculation yielded rotational constants within 0.1% of the experimental values.

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

    SciTech Connect

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

    2014-04-01

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

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

    SciTech Connect

    Ojeda, Manuel; Iglesia, Enrique

    2008-11-24

    Formic acid (HCOOH) is a convenient hydrogen carrier in fuel cells designed for portable use. Recent studies have shown that HCOOH decomposition is catalyzed with Ru-based complexes in the aqueous phase at near-ambient temperatures. HCOOH decomposition reactions are used frequently to probe the effects of alloying and cluster size and of geometric and electronic factors in catalysis. These studies have concluded that Pt is the most active metal for HCOOH decomposition, at least as large crystallites and extended surfaces. The identity and oxidation state of surface metal atoms influence the relative rates of dehydrogenation (HCOOH {yields} H{sub 2} + CO{sub 2}) and dehydration (HCOOH {yields} H{sub 2}O + CO) routes, a selectivity requirement for the synthesis of CO-free H{sub 2} streams for low-temperature fuel cells. Group Ib and Group VIII noble metals catalyze dehydrogenation selectively, while base metals and metal oxides catalyze both routes, either directly or indirectly via subsequent water-gas shift (WGS) reactions.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  20. Theoretical Study of Shocked Formic Acid: Born-Oppenheimer MD Calculations of the Shock Hugoniot and Early-Stage Chemistry.

    PubMed

    Rice, Betsy M; Byrd, Edward F C

    2016-03-01

    Quantum and classical molecular dynamics simulations are used to explore whether chemical reactivity of shocked formic acid occurs at pressures greater than 15 GPa, a question arising from results of different shock compression experiments. The classical molecular dynamics simulations were performed using a quantum-based nonreactive pair additive interaction potential whereas the full resolution quantum mechanical molecular dynamics simulations allow chemical reactions. Although the shock Hugoniot curve calculated using nonreactive classical MD for formic acid is in reasonable agreement with one set of experimental results, shock Hugoniot points calculated using Born-Oppenheimer MD at 30 GPa are in agreement with the set of experimental data that suggests chemical reactivity at these elevated temperatures and pressures. Examination of atomic positions throughout the Born-Oppenheimer MD trajectories clearly indicates extensive and complex chemical reaction, chiefly involving hydrogen-atom transfer and intermolecular complexation. PMID:26654191

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

    PubMed

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

    2014-06-01

    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

  2. Photocatalytic CO2 reduction to formic acid using a Ru(II)-Re(I) supramolecular complex in an aqueous solution.

    PubMed

    Nakada, Akinobu; Koike, Kazuhide; Nakashima, Takuya; Morimoto, Tatsuki; Ishitani, Osamu

    2015-02-16

    In an aqueous solution, photophysical, photochemical, and photocatalytic abilities of a Ru(II)-Re(I) binuclear complex (RuReCl), of which Ru(II) photosensitizer and Re(I) catalyst units were connected with a bridging ligand, have been investigated in details. RuReCl could photocatalyze CO2 reduction using ascorbate as an electron donor, even in an aqueous solution. The main product of the photocatalytic reaction was formic acid in the aqueous solution; this is very different in product distribution from that in a dimethylformamide (DMF) and triethanolamine (TEOA) mixed solution in which the main product was CO. A (13)CO2 labeling experiment clearly showed that formic acid was produced from CO2. The turnover number and selectivity of the formic acid production were 25 and 83%, respectively. The quantum yield of the formic acid formation was 0.2%, which was much lower, compared to that in the DMF-TEOA mixed solution. Detail studies of the photochemical electron-transfer process showed back-electron transfer from the one-electron-reduced species (OERS) of the photosensitizer unit to an oxidized ascorbate efficiently proceeded, and this should be one of the main reasons why the photocatalytic efficiency was lower in the aqueous solution. In the aqueous solution, ligand substitution of the Ru(II) photosensitizer unit proceeded during the photocatalytic reaction, which was a main deactivation process of the photocatalytic reaction. The product of the ligand substitution was a Ru(II) bisdiimine complex or complexes with ascorbate as a ligand or ligands. PMID:25654586

  3. Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions.

    PubMed

    Metin, Önder; Sun, Xiaolian; Sun, Shouheng

    2013-02-01

    Monodisperse 4 nm AuPd alloy nanoparticles with controlled composition were synthesized by co-reduction of hydrogen tetrachloroaurate(III) hydrate and palladium(II) acetylacetonate with a borane-morpholine complex in oleylamine. These NPs showed high activity (TOF = 230 h(-1)) and stability in catalyzing formic acid dehydrogenation and hydrogen production in water at 50 °C without any additives. PMID:23254519

  4. Formic acid electro-oxidation at PtAu alloyed nanoparticles synthesized by pulsed laser ablation in liquids

    NASA Astrophysics Data System (ADS)

    Oko, Daniel Nii; Zhang, Jianming; Garbarino, Sébastien; Chaker, Mohamed; Ma, Dongling; Tavares, Ana C.; Guay, Daniel

    2014-02-01

    A series of mono dispersed PtxAu100-x alloy nanoparticles (NPs), with x varying from 0 to 100, were prepared by pulsed laser ablation in liquids, using a series of targets that were made by mixing pure Pt and pure Au powders. The structures of PtxAu100-x alloy NPs were assessed by transmission electron microscopy and X-ray diffraction. A face-centered solid solution is obtained over the whole composition range, and the particle size increases from 2.5 to 5.3 nm as x is increased from 0 to 100. The electrocatalytic performances of the PtxAu100-x alloy NPs towards the formic acid oxidation were investigated by cyclic voltammetry and chronoamperometry. On as-prepared PtxAu100-x alloy NPs, oxidation of formic acid occurs through dehydrogenation, while dehydration is the privileged mechanism on as-prepared mixtures of Pt and Au NPs. However, after a series of CV in 0.5 M H2SO4, both types of catalysts are able to oxidize formic acid according to the dehydrogenation pathway. After 600 s of electrolysis, the mass activities of PtxAu100-x alloy NPs is a factor of two larger than that of mixtures of pure Pt and pure Au NPs with the same surface composition, although both types of catalysts display similar activity with respect to the total electrochemically active surface area.

  5. Ligand-induced substrate steering and reshaping of [Ag2(H)](+) scaffold for selective CO2 extrusion from formic acid.

    PubMed

    Zavras, Athanasios; Khairallah, George N; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A J

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)](+) by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)](+) and [Ph3PAg2(H)](+) react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)](+) is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)(+) scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)](+) and H2. Decarboxylation of [dppmAg2(O2CH)](+) via CID regenerates [dppmAg2(H)](+). These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  6. Photocatalytic Formic Acid Conversion on CdS Nanocrystals with Controllable Selectivity for H2 or CO**

    PubMed Central

    Kuehnel, Moritz F; Wakerley, David W; Orchard, Katherine L; Reisner, Erwin

    2015-01-01

    Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon-neutral economy. We present an inexpensive system for the selective room-temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible-light irradiation (λ>420 nm, 1 sun), suspensions of ligand-capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H2 gcat−1 h−1 with >99 % selectivity when combined with a cobalt co-catalyst; the quantum yield at λ=460 nm was 21.2±2.7 %. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO gcat−1 h−1 with >95 % selectivity and 19.7±2.7 % quantum yield. H2 and CO production was sustained for more than one week with turnover numbers greater than 6×105 and 3×106, respectively. PMID:26201752

  7. Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid

    PubMed Central

    Zavras, Athanasios; Khairallah, George N.; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J.; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A. J.

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)]+ by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)]+ and [Ph3PAg2(H)]+ react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)]+ is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)+ scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)]+ and H2. Decarboxylation of [dppmAg2(O2CH)]+ via CID regenerates [dppmAg2(H)]+. These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  8. Anode modification with formic acid: A simple and effective method to improve the power generation of microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Liu, Weifeng; Cheng, Shaoan; Guo, Jian

    2014-11-01

    The physicochemical properties of anode material directly affect the anodic biofilm formation and electron transfer, thus are critical for the power generation of microbial fuel cells (MFCs). In this work, carbon cloth anode was modified with formic acid to enhance the power production of MFCs. Formic acid modification of anode increased the maximum power density of a single-chamber air-cathode MFC by 38.1% (from 611.5 ± 6 mW/m2 to 877.9 ± 5 mW/m2). The modification generated a cleaner electrode surface and a reduced content of oxygen and nitrogen groups on the anode. The surface changes facilitated bacterial growth on the anode and resulted in an optimized microbial community. Thus, the electron transfer rate on the modified anodes was enhanced remarkably, contributing to a higher power output of MFCs. Anode modification with formic acid could be an effective and simple method for improving the power generation of MFCs. The modification method holds a huge potential for large scale applications and is valuable for the scale-up and commercialization of microbial fuel cells.

  9. Photocatalytic Formic Acid Conversion on CdS Nanocrystals with Controllable Selectivity for H2 or CO.

    PubMed

    Kuehnel, Moritz F; Wakerley, David W; Orchard, Katherine L; Reisner, Erwin

    2015-08-10

    Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon-neutral economy. We present an inexpensive system for the selective room-temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible-light irradiation (λ>420 nm, 1 sun), suspensions of ligand-capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H2 g(cat)(-1) h(-1) with >99% selectivity when combined with a cobalt co-catalyst; the quantum yield at λ=460 nm was 21.2±2.7%. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO g(cat)(-1) h(-1) with >95% selectivity and 19.7±2.7% quantum yield. H2 and CO production was sustained for more than one week with turnover numbers greater than 6×10(5) and 3×10(6), respectively. PMID:26201752

  10. Understanding the enhanced catalytic activity of Cu1@Pd3(111) in formic acid dissociation, a theoretical perspective

    NASA Astrophysics Data System (ADS)

    He, Feng; Li, Kai; Xie, Guangyou; Wang, Ying; Jiao, Menggai; Tang, Hao; Wu, Zhijian

    2016-06-01

    The bimetallic Cu1@Pd3(111) catalyst has been synthesized recently and exhibits better catalytic activity and durability compared with pure Pd(111) as anode catalyst in direct formic acid fuel cells (DFAFCs). In this work, we studied the reaction mechanism of formic acid dissociation on both Pd(111) and Cu1@Pd3(111) by using the density functional method. Our calculations showed that the surface adsorption of the poisoning species CO on Cu1@Pd3(111) is weakened mainly by the strain effect rather than the Cusbnd Pd ligand effect. The Cu1@Pd3(111) can effectively promote the catalytic activity for formic acid dissociation by decreasing the barrier of CO2 formation from the preferential trans-COOH intermediate and increasing the barrier of CO formation from the reduction of CO2. We found that the H atom accumulation, electron accumulation and low electrode potential could accelerate the catalyst deactivation due to the contamination of the poisoning species CO. Furthermore, under low anode potential, the Cu1@Pd3(111) has better durability than pure Pd(111), which can be attributed to the unfavorable CO formation and the favorable CO desorption.

  11. Ambient formic acid in southern California air: A comparison of two methods, Fourier transform infrared spectroscopy and alkaline trap-liquid chromatography with UV detection

    SciTech Connect

    Grosjean, D. ); Tuazon, E.C. ); Fujita, E. )

    1990-01-01

    Formic acid is an ubiquitous component of urban smog. Sources of formic acid in urban air include direct emissions from vehicles and in situ reaction of ozone with olefins. Ambient levels of formic acid in southern California air were first measured some 15 years ago by Hanst et al. using long-path Fourier transform infrared spectroscopy (FTIR). All subsequent studies of formic acid in the Los Angeles area have involved the use of two methods, either FTIR or collection on alkaline traps followed by gas chromatography, ion chromatography, or liquid chromatography analysis with UV detection, ATLC-UV. The Carbon Species Methods Comparison Study (CSMCS), a multilaboratory air quality study carried out in August 1986 at a southern California smog receptor site, provided an opportunity for direct field comparison of the FTIR and alkaline trap methods. The results of the comparison are presented in this brief report.

  12. Exchange of atmospheric formic and acetic acids with trees and crop plants under controlled chamber and purified air conditions

    NASA Astrophysics Data System (ADS)

    Kesselmeier, J.; Bode, K.; Gerlach, C.; Jork, E.-M.

    We investigated the exchange of formic and acetic acids between the atmosphere and various tree species such as beech ( Fagus sylvatica L.), ash ( Fraxinus excelsior L.), spruce ( Picea abies L.) Karst, holm oak ( Quercus ilex L.), and birch ( Betula pendula L.). and some crop-plant species such as corn ( Zea mays, var. Banjo), pea ( Pisum sativum, var. Solara), barley ( Hordeum vulgare, var. Igri) and oat (Avena sativa, var. Wiesel). All experiments were done with dynamic enclosures flushed with purified oxidant-free air, containing only low or controlled amounts of the two acids. Significant and light-triggered emission of both acids from all tree species was observed. For one tree species (ash) a seasonal large increase in fall due to early leaf decomposition was found. The standard emission factors (30°C and PAR=1000 μmol m 2 s -1) given as (nmol m -2 min -1) for acetic and formic acids, respectively, were 8.1 and 29.7 (ash, autumn), 1.0 and 3.3 (ash, summer), 0.9 and 1.4 (beech), 0.7 and 1.45 (spruce), 1.9 and 2.4 (Holm oak) and 1.7 and 6.7 (birch). Rough estimation of global annual emissions range between 20 and 130 Gmol formic acid and 10 and 33 Gmol acetic acid. These numbers reflect a 15-30% contribution by forest emissions to the continental organic acid budget. As compared to the global total NMHC emissions low molecular weight organic acids are of minor importance. In contrast to the trees, none of the crop-plant species investigated showed an emission, but always a clear deposition of both acids. Both emission from trees as well as uptake by the agricultural plants could be related to transpiration rates and leaf conductances.

  13. Quantification and evidence for mechanically metered release of pygidial secretions in formic acid-producing carabid beetles.

    PubMed

    Will, Kipling W; Gill, Aman S; Lee, Hyeunjoo; Attygalle, Athula B

    2010-01-01

    This study is the first to measure the quantity of pygidial gland secretions released defensively by carabid beetles (Coleoptera: Carabidae) and to accurately measure the relative quantity of formic acid contained in their pygidial gland reservoirs and spray emissions. Individuals of three typical formic acid producing species were induced to repeatedly spray, ultimately exhausting their chemical compound reserves. Beetles were subjected to faux attacks using forceps and weighed before and after each ejection of chemicals. Platynus brunneomarginatus (Mannerheim) (Platynini), P. ovipennis (Mannerheim) (Platynini) and Calathus ruficollis Dejean (Sphodrini), sprayed average quantities with standard error of 0.313 +/- 0.172 mg, 0.337 +/- 0.230 mg, and 0.197 +/- 0.117 mg per spray event, respectively. The quantity an individual beetle released when induced to spray tended to decrease with each subsequent spray event. The quantity emitted in a single spray was correlated to the quantity held in the reservoirs at the time of spraying for beetles whose reserves are greater than the average amount emitted in a spray event. For beetles with a quantity less than the average amount sprayed in reserve there was no significant correlation. For beetles comparable in terms of size, physiological condition and gland reservoir fullness, the shape of the gland reservoirs and musculature determined that a similar effort at each spray event would mechanically meter out the release so that a greater amount was emitted when more was available in the reservoir. The average percentage of formic acid was established for these species as 34.2%, 73.5% and 34.1% for for P. brunneomarginatus, P. ovipennis and C. ruficollis, respectively. The average quantities of formic acid released by individuals of these species was less than two-thirds the amount shown to be lethal to ants in previously published experiments. However, the total quantity from multiple spray events from a single individual

  14. Quantification and Evidence for Mechanically Metered Release of Pygidial Secretions in Formic Acid-Producing Carabid Beetles

    PubMed Central

    Will, Kipling W.; Gill, Aman S.; Lee, Hyeunjoo; Attygalle, Athula B.

    2010-01-01

    This study is the first to measure the quantity of pygidial gland secretions released defensively by carabid beetles (Coleoptera: Carabidae) and to accurately measure the relative quantity of formic acid contained in their pygidial gland reservoirs and spray emissions. Individuals of three typical formic acid producing species were induced to repeatedly spray, ultimately exhausting their chemical compound reserves. Beetles were subjected to faux attacks using forceps and weighed before and after each ejection of chemicals. Platynus brunneomarginatus (Mannerheim) (Platynini), P. ovipennis (Mannerheim) (Platynini) and Calathus ruficollis Dejean (Sphodrini), sprayed average quantities with standard error of 0.313 ± 0.172 mg, 0.337 ± 0.230 mg, and 0.197 ± 0.117 mg per spray event, respectively. The quantity an individual beetle released when induced to spray tended to decrease with each subsequent spray event. The quantity emitted in a single spray was correlated to the quantity held in the reservoirs at the time of spraying for beetles whose reserves are greater than the average amount emitted in a spray event. For beetles with a quantity less than the average amount sprayed in reserve there was no significant correlation. For beetles comparable in terms of size, physiological condition and gland reservoir fullness, the shape of the gland reservoirs and musculature determined that a similar effort at each spray event would mechanically meter out the release so that a greater amount was emitted when more was available in the reservoir. The average percentage of formic acid was established for these species as 34.2%, 73.5% and 34.1% for for P. brunneomarginatus, P. ovipennis and C. ruficollis, respectively. The average quantities of formic acid released by individuals of these species was less than two-thirds the amount shown to be lethal to ants in previously published experiments. However, the total quantity from multiple spray events from a single individual could

  15. Formic and Acetic Acid Observations over Colorado by Chemical Ionization Mass Spectrometry and Organic Acids' Role in Air Quality

    NASA Astrophysics Data System (ADS)

    Treadaway, V.; O'Sullivan, D. W.; Heikes, B.; Silwal, I.; McNeill, A.

    2015-12-01

    Formic acid (HFo) and acetic acid (HAc) have both natural and anthropogenic sources and a role in the atmospheric processing of carbon. These organic acids also have an increasing importance in setting the acidity of rain and snow as precipitation nitrate and sulfate concentrations have decreased. Primary emissions for both organic acids include biomass burning, agriculture, and motor vehicle emissions. Secondary production is also a substantial source for both acids especially from biogenic precursors, secondary organic aerosols (SOAs), and photochemical production from volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs). Chemical transport models underestimate organic acid concentrations and recent research has sought to develop additional production mechanisms. Here we report HFo and HAc measurements during two campaigns over Colorado using the peroxide chemical ionization mass spectrometer (PCIMS). Iodide clusters of both HFo and HAc were recorded at mass-to-charge ratios of 173 and 187, respectively. The PCIMS was flown aboard the NCAR Gulfstream-V platform during the Deep Convective Clouds and Chemistry Experiment (DC3) and aboard the NCAR C-130 during the Front Range Air Pollution and Photochemistry Experiment (FRAPPE). The DC3 observations were made in May and June 2012 extending from the surface to 13 km over the central and eastern United States. FRAPPE observations were made in July and August 2014 from the surface to 7 km over Colorado. DC3 measurements reported here are focused over the Colorado Front Range and complement the FRAPPE observations. DC3 HFo altitude profiles are characterized by a decrease up to 6 km followed by an increase either back to boundary layer mixing ratio values or higher (a "C" shape). Organic acid measurements from both campaigns are interpreted with an emphasis on emission sources (both natural and anthropogenic) over Colorado and in situ photochemical production especially ozone precursors.

  16. Oxidation of formic acid by oxyanions of chlorine and its implications to the Viking Labeled Release experiment

    NASA Astrophysics Data System (ADS)

    Martinez, P.; Navarro-gonzalez, R.

    2013-05-01

    The Viking Landers that arrived on Mars in 1976 carried out three biological experiments designed to investigate if there was microbial life. These were the Gas-Exchange, Pyrolitic Release and Labeled Release experiments. The three experiments yielded positive responses but the Labeled Release experiment had a kinetic response indicative of microbial activity. The experiment consisted of adding a broth of nutrients (formic acid, glycolic acid, glycine, D- and L-alanine and D- and L-lactic acid uniformly marked with 14C) to martian soil samples. The results were surprising; the nutrients were consumed releasing radioactive gases in a manner that is compatible by terrestrial microorganisms. The existence of Martian life was contradicted by soil chemical analysis that indicated the absence of organic compounds above the detection limits of parts per billion (ppb). Instead the positive response of the Labeled Release Experiment was attributed to the existence of peroxides and/or superoxides in the Martian soils that destroyed the nutrients upon contact. Recently, the Phoenix mission that landed in the Martian Arctic in 2008 revealed the presence of a highly oxidized form of the element chlorine in the soil: perchlorate. Perchlorate is thought to have formed in the Martian atmosphere by the oxidation of chloride from volcanic sources with ozone. Therefore perchlorate is formed by the stepwise oxidation of hypochlorite, chlorite and chlorate. These oxyanions of chlorine are powerful oxidizers that may exist in the Martian soil and may have reacted with the nutrients of the Labeled Release Experiment. This paper aims to better understand these results by designing experiments to determine the kinetics of decomposition of formic acid to carbon dioxide with different oxidized forms of chlorine by headspace technique in gas chromatography coupled to mass spectrometry (GC / MS). Previous studies done in the laboratory showed that only hypochlorite quantitatively reacted with

  17. Species differences in methanol and formic acid pharmacokinetics in mice, rabbits and primates

    SciTech Connect

    Sweeting, J. Nicole; Siu, Michelle; McCallum, Gordon P.; Miller, Lutfiya; Wells, Peter G.

    2010-08-15

    Methanol (MeOH) is metabolized primarily by alcohol dehydrogenase in humans, but by catalase in rodents, with species variations in the pharmacokinetics of its formic acid (FA) metabolite. The teratogenic potential of MeOH in humans is unknown, and its teratogenicity in rodents may not accurately reflect human developmental risk due to differential species metabolism, as for some other teratogens. To determine if human MeOH metabolism might be better reflected in rabbits than rodents, the plasma pharmacokinetics of MeOH and FA were compared in male CD-1 mice, New Zealand white rabbits and cynomolgus monkeys over time (24, 48 and 6 h, respectively) following a single intraperitoneal injection of 0.5 or 2 g/kg MeOH or its saline vehicle. Following the high dose, MeOH exhibited saturated elimination kinetics in all 3 species, with similar peak concentrations and a 2.5-fold higher clearance in mice than rabbits. FA accumulation within 6 h in primates was 5-fold and 43-fold higher than in rabbits and mice respectively, with accumulation being 10-fold higher in rabbits than mice. Over 48 h, FA accumulation was nearly 5-fold higher in rabbits than mice. Low-dose MeOH in mice and rabbits resulted in similarly saturated MeOH elimination in both species, but with approximately 2-fold higher clearance rates in mice. FA accumulation was 3.8-fold higher in rabbits than mice. Rabbits more closely than mice reflected primates for in vivo MeOH metabolism, and particularly FA accumulation, suggesting that developmental studies in rabbits may be useful for assessing potential human teratological risk.

  18. Photo-assisted Enhancement of Formic Acid Oxidation over Platinized TiO2 Nanotube Composite

    NASA Astrophysics Data System (ADS)

    Mojumder, Nazrul I.

    1D TiO2 nanotubes (TNT) prepared by anodization deposited with 0D Pt nanoparticles (TNT--PT) prepared by a solvothermal method is used as a photoelectrocatalyst for formic acid (FA) oxidation. SEM, XRD, absorbance, EDX analysis indicates the polycrystalline TiO2 nanotubes of approximately 100+/-10 nm in diameter with 5--25 nm dimensions of Pt aggregates are formed. The composite was tested as a working electrode in the photoelectrooxidation of FA for applications such as fuel cells. Electrochemical characterization of the synthesized electrode was studied under the effect of light in order to determine the current generation of the photoactive electrode. The results show that Pt coupled with TiO 2 leads to a synergistic, i.e. boosting effect, in the increase of current density. In the presence of light, there is about a 5--fold increase in current density (75.1 mA/cm2) as compared to the absence of light (16.0 mA/cm 2). At a bias of 0.45 V the increase is about 20--fold in the presence of light (62.5 mA/cm2) compared to (3.04 mA/cm 2) in the absence of light. In addition, the effect of light in the current generation as a result of voltage bias effect is shown, thus leading to the observation that the longer the working electrode encounters light, the greater number of electrons that are generated to yield a higher current density. The study of this effect indicates a progressive current generation from light off to light on, traversing the whole range of the current generation. Thus, a combination of Helmholtz electrical double layer based limitation and mass transport limitations determine the extent of this boosting phenomenon.

  19. Ecosystem-scale compensation points of formic and acetic acid in the central Amazon

    NASA Astrophysics Data System (ADS)

    Jardine, K.; Yañez Serrano, A.; Arneth, A.; Abrell, L.; Jardine, A.; Artaxo, P.; Alves, E.; Kesselmeier, J.; Taylor, T.; Saleska, S.; Huxman, T.

    2011-09-01

    Organic acids, central to terrestrial carbon metabolism and atmospheric photochemistry, are ubiquitous in the troposphere in the gas, particle, and aqueous phases. As the dominant organic acids in the atmosphere, formic acid (FA, HCOOH) and acetic acid (AA, CH3COOH) control precipitation acidity in remote regions and may represent a critical link between the terrestrial carbon and water cycles by acting as key intermediates in plant carbon and energy metabolism and aerosol-cloud-precipitation interactions. However, our understanding of the exchange of these acids between terrestrial ecosystems and the atmosphere is limited by a lack of field observations, the existence of biogenic and anthropogenic primary and secondary sources whose relative importance is unclear, and the fact that vegetation can act as both a source and a sink. Here, we first present data obtained from the tropical rainforest mesocosm at Biosphere 2 which isolates primary vegetation sources. Strong light and temperature dependent emissions enriched in FA relative to AA were simultaneously observed from individual branches (FA/AA = 2.1 ± 0.6) and mesocosm ambient air (FA/AA = 1.4 ± 0.3). We also present long-term observations of vertical concentration gradients of FA and AA within and above a primary rainforest canopy in the central Amazon during the 2010 dry and 2011 wet seasons. We observed a seasonal switch from net ecosystem-scale deposition during the dry season to net emissions during the wet season. This switch was associated with reduced ambient concentrations in the wet season (FA < 1.3 nmol mol-1, AA < 2.0 nmol mol-1) relative to the dry season (FA up to 3.3 nmol mol-1, AA up to 6.0 nmol mol-1), and a simultaneous increase in the FA/AA ambient concentration ratios from 0.3-0.8 in the dry season to 1.0-2.1 in the wet season. These observations are consistent with a switch between a biomass burning dominated source in the dry season (FA/AA < 1.0) to a vegetation dominated source in the

  20. Ecosystem-Scale Compensation Point Analysis of Formic and Acetic Acid in the Central Amazon

    NASA Astrophysics Data System (ADS)

    Yanez-Serrano, A. M.; Jardine, K. J.; Arneth, A.; Abrell, L.; Jardine, A. B.; Artaxo, P.; Gomes, E.; Kesselmeier, J.; Saleska, S. R.; Huxman, T. E.

    2011-12-01

    Organic acids, central to terrestrial carbon metabolism and atmospheric photochemistry, are ubiquitous in the troposphere in the gas, particle, and aqueous phases. As the dominant organic acids in the atmosphere, formic acid (FA, HCOOH) and acetic acid (AA, CH3COOH) control precipitation acidity in remote regions and may represent a critical link between the terrestrial carbon and water cycles by acting as key intermediates in plant carbon and energy metabolism and aerosol-cloud-precipitation interactions. However, our understanding of the exchange of these acids between terrestrial ecosystems and the atmosphere is limited by a lack of field observations, the existence of biogenic and anthropogenic primary and secondary sources whose relative importance is unclear, and the fact that vegetation can act as both a source and a sink. Here, we present results from the tropical rainforest mescosom at Biosphere 2 which isolates primary vegetation sources. Strong light and temperature dependent emissions of FA and AA were simultaneously observed from individual branches and mesocosm ambient air with a strong enrichment in FA (FA/AA = 1.4 +/- 0.3, R2 of 0.89 +/- 0.10). We also present long-term observations of vertical concentration gradients of FA and AA within and above a primary rainforest canopy in central Amazonia during the 2010 dry and 2011 wet seasons. We observed a seasonal switch from net ecosystem-scale deposition during the dry season to net emissions during the wet season. This switch was associated with reduced ambient concentrations in the wet season (FA < 1.3 ppbv, AA < 2.0 ppbv) relative to the dry season (FA up to 3.3 ppbv, AA up to 6.0 ppbv), and a simultaneous increase in the FA/AA ambient concentration ratios from 0.3-0.8 in the dry season to 1.0-2.1 in the wet season. These observations are consistent with a switch between a biomass burning dominated source in the dry season (FA/AA < 1.0) to a vegetation dominated source in the wet season and call into

  1. Ecosystem-scale compensation points of formic and acetic acid in the central Amazon

    NASA Astrophysics Data System (ADS)

    Jardine, K.; Yañez Serrano, A.; Arneth, A.; Abrell, L.; Jardine, A.; Artaxo, P.; Alves, E.; Kesselmeier, J.; Taylor, T.; Saleska, S.; Huxman, T.

    2011-12-01

    Organic acids, central to terrestrial carbon metabolism and atmospheric photochemistry, are ubiquitous in the troposphere in the gas, particle, and aqueous phases. As the dominant organic acids in the atmosphere, formic acid (FA, HCOOH) and acetic acid (AA, CH3COOH) control precipitation acidity in remote regions and may represent a critical link between the terrestrial carbon and water cycles by acting as key intermediates in plant carbon and energy metabolism and aerosol-cloud-precipitation interactions. However, our understanding of the exchange of these acids between terrestrial ecosystems and the atmosphere is limited by a lack of field observations, the existence of biogenic and anthropogenic primary and secondary sources whose relative importance is unclear, and the fact that vegetation can act as both a source and a sink. Here, we first present data obtained from the tropical rainforest mesocosm at Biosphere 2 which isolates primary vegetation sources. Strong light and temperature dependent emissions enriched in FA relative to AA were simultaneously observed from individual branches (FA/AA = 3.0 ± 0.7) and mesocosm ambient air (FA/AA = 1.4 ± 0.3). We also present long-term observations of vertical concentration gradients of FA and AA within and above a primary rainforest canopy in the central Amazon during the 2010 dry and 2011 wet seasons. We observed a seasonal switch from net ecosystem-scale deposition during the dry season to net emissions during the wet season. This switch was associated with reduced ambient concentrations in the wet season (FA < 1.3 nmol mol-1, AA < 2.0 nmol mol-1) relative to the dry season (FA up to 3.3 nmol mol-1, AA up to 6.0 nmol mol-1), and a simultaneous increase in the FA/AA ambient concentration ratios from 0.3-0.8 in the dry season to 1.0-2.1 in the wet season. These observations are consistent with a switch between a biomass burning dominated source in the dry season (FA/AA < 1.0) to a vegetation dominated source in the

  2. Is the reaction between formic acid and protonated aminomethanol a possible source of glycine precursors in the interstellar medium?

    NASA Astrophysics Data System (ADS)

    Redondo, Pilar; Largo, Antonio; Barrientos, Carmen

    2015-07-01

    Context. One of the most interesting questions in interstellar chemistry concerns whether we can detect the basic building blocks of proteins in astronomical sources. In ascertaining whether amino acids could be possible interstellar molecules, a crucial point is how they could be synthesized in the interstellar medium. Aims: We do a theoretical study of the ion-molecule reaction involving protonated aminomethanol and formic acid to establish its viability in space. This ion-molecule reaction has been proposed by other authors as a possible way to produce glycine in the interstellar medium. Methods: The relevant stationary points on the potential energy surface of the reaction between protonated aminomethanol and formic acid have been theoretically studied by using ab initio methods. The second-order Moller-Plesset level was employed, in conjunction with the correlation-consistent polarized valence triple-zeta (cc-pVTZ) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) on the MP2/cc-pVTZ geometries with the aug-cc-pVTZ basis set. Results: Formation of protonated glycine is an exothermic process; however, the process presents a net activation barrier that makes this reaction unfeasible under interstellar conditions. Conclusions: The reaction of protonated aminomethanol with formic acid does not seem to be a plausible source of interstellar glycine. This particular case is a clear example that a detailed study of the potential energy surface is needed to establish the relevance of a process in the interstellar medium.

  3. The effects of temperature and dose of formic acid on treatment efficacy against Varroa destructor (Acari: Varroidae), a parasite of Apis mellifera (Hymenoptera: Apidae).

    PubMed

    Underwood, Robyn M; Currie, Robert W

    2003-01-01

    In order to decrease the variability of formic acid treatments against the honey bee parasite the varroa mite, Varroa destructor (Anderson and Trueman 2000), it is necessary to determine the dose-time combination that best controls mites without harming bees. The concentration x time (CT) product is a valuable tool for studying fumigants and how they might perform under various environmental conditions. This laboratory study is an assessment of the efficacy of formic acid against the varroa mite under a range of formic acid concentrations and temperatures. The objectives are 1) to determine the effect of temperature and dose of formic acid on worker honey bee and varroa mite survival, 2) to determine the CT50 products for both honey bees and varroa mites and 3) to determine the best temperature and dose to optimize selectivity of formic acid treatment for control of varroa mites. Worker honey bees and varroa mites were fumigated at 0, 0.01, 0.02, 0.04, 0.08, and 0.16 mg/L at 5, 15, 25, and 35 degrees C for 12 d. Mite and bee mortality were assessed at regular intervals. Both mite and bee survival were affected by formic acid dose. Doses of 0.08 and 0.16 mg/L were effective at killing mites at all temperatures tested above 5 degrees C. There was a significant interaction between temperature, dose, and species for the CT50 product. The difference between the CT50 product of bees and mites was significant at only a few temperature-dose combinations. CT product values showed that at most temperatures the greatest fumigation efficiency occurred at lower doses of formic acid. However, the best fumigation efficiency and selectivity combination for treatments occurred at a dose of 0.16 mg/L when the temperature was 35 degrees C. PMID:14635816

  4. Antibacterial activity of formic and propionic acids in the diet of hens on Salmonellas in the crop.

    PubMed

    Thompson, J L; Hinton, M

    1997-03-01

    1. The inclusion of formic and propionic acids in the form of Bio-Add to the food of hens made no difference to the pH of the intestinal tract, but resulted in higher concentrations of these acids in the contents of the crop and gizzard. 2. Organic acids in the crop contents were bactericidal for Salmonella serotype Enteritidis PT4 in vitro, and also caused sub-lethal damage because fewer cells were recovered on selective salmonella media (brilliant green phenol red agar) than on non-selective media (nutrient agar). 3. Inclusion of Bio-Add in the food at 12g/kg may reduce the number of lactic acid-producing bacteria in the crop, and hence the amount of naturally produced organic acids. PMID:9088614

  5. Effect of plant extracts and formic acid on the intestinal equilibrium of early-weaned pigs.

    PubMed

    Manzanilla, E G; Perez, J F; Martin, M; Kamel, C; Baucells, F; Gasa, J

    2004-11-01

    We evaluated the effects of a plant extracts mixture (XT) standardized in 5% (wt/wt) carvacrol, 3% cinnamaldehyde, and 2% capsicum oleoresin (oregano, cinnamon and Mexican pepper), alone or in combination with formic acid (FA), on the productive performance and the intestinal ecosystem of the early-weaned pig. Pigs weaned at 20 +/- 1 d of age (n = 216) were allocated in 24 pens and fed a standard medicated prestarter diet for 12 d. Twelve days after weaning, a stress management system based on social and dietary stress factors was applied to the animals, after which, each group was allocated to one of six dietary treatments, which followed a factorial arrangement, with three levels (as-fed basis) of the XT (0, 150, and 300 mg/kg) and two levels of FA (0 and 0.5%). On d 24 and 25 after the stress episode, eight pigs per treatment were killed to examine variables describing some aspects of the gastrointestinal ecology. Two days after the stress episode, an Escherichia coli K88 diarrhea episode occurred, and five casualties were registered. Four of the five deaths occurred in pens of pigs not fed the XT. The FA resulted in better G:F (P = 0.040) in coincidence with shorter villous height (P = 0.073) and lower rectal total microbial mass (P = 0.078). Both XT and FA addition increased stomach content (P = 0.006 and 0.003, respectively) and percentage of DM (P = 0.089 and 0.010, respectively), suggesting an increased gastric retention time; consequently, pH was also increased (P = 0.005 and 0.060, respectively). The XT decreased ileum total microbial mass (P = 0.025) and increased the lactobacilli:enterobacteria ratio (P = 0.002). The VFA profile in the cecum and colon was modified by XT inclusion, increasing the proportion of acetate (P = 0.018 and 0.025, respectively) and diminishing the proportion of butyrate (P = 0.096 and 0.040, respectively) and valerate (P = 0.001 and 0.039, respectively). Both XT and FA were shown to be effective in modifying the gastrointestinal

  6. Red- and blue-shifted hydrogen bonds in the cis-trans noncyclic formic acid dimer.

    PubMed

    Zhou, Pan-Pan; Qiu, Wen-Yuan

    2009-08-01

    The cis-trans noncyclic formic acid dimer was studied by means of MP2 method with 6-31G(d,p), 6-31+G(d,p) and 6-311+G(d,p) basis sets. It exhibits simultaneously red-shifted O-H...O and blue-shifted C-H...O hydrogen bonds. AIM and NBO analyses are performed at the MP2/6-31+G(d,p) level to explore their properties and origins. AIM analysis provides the evidence that the O-H bond becomes weaker and the C-H bond becomes stronger upon the hydrogen bond formations. Intermolecular and intramolecular hyperconjugations have important influence on the electron densities in the X-H (X = O, C) sigma bonding orbital and its sigma* antibonding orbital. The electron densities in the two orbitals are closely connected with the X-H (X = O, C) bond length, and they are used to quantitatively estimate the bond length variation. The larger amount of charge transfer in the red-shifted O-H...O hydrogen bond is due to its favorable H...O electron channel, whereas the H...O electron channel in the blue-shifted C-H...O hydrogen bond is weaker. Structural reorganization effects shorten the C-H bond by approximately 30% when compared to the C-H bond contraction upon the dimerization. Strikingly, it leads to a small elongation and a slight red shift of the O-H bond. Both rehybridization and repolarization result in the X-H (X = O, C) bond contraction, but their effects on the O-H bond do not hold a dominant position. The hydrogen-bonding processes go through the electrostatic attractions, van der Waals interactions, charge-transfer interactions, hydrogen-bonding interactions and electrostatic repulsions. Electrostatic attractions are of great importance on the origin of the red-shifted O-H...O hydrogen bond, especially the strong H(delta+)...O(delta-) attraction. For the blue-shifted C-H...O hydrogen bond, the considerable nucleus-nucleus repulsion between H and O atoms caused by the strong electrostatic attraction between C and O atoms is a possible reason for the C-H bond contraction and

  7. Short-term fumigation of honey bee (Hymenoptera: Apidae) colonies with formic and acetic acids for the control of Varroa destructor (Acari: Varroidae).

    PubMed

    vanEngelsdorp, Dennis; Underwood, Robyn M; Cox-Foster, Diana L

    2008-04-01

    Controlling populations of varroa mites is crucial for the survival of the beekeeping industry. Many treatments exist, and all are designed to kill mites on adult bees. Because the majority of mites are found under capped brood, most treatments are designed to deliver active ingredients over an extended period to control mites on adult bees, as developing bees and mites emerge. In this study, a 17-h application of 50% formic acid effectively killed mites in capped worker brood and on adult bees without harming queens or uncapped brood. Neither acetic acid nor a combined treatment of formic and acetic acids applied to the West Virginia formic acid fumigator was as effective as formic acid alone in controlling varroa mites. In addition, none of the treatments tested in late summer had an effect on the late-season prevalence of deformed wing virus. The short-term formic acid treatment killed > 60% of varroa mites in capped worker brood; thus, it is a promising tool for beekeepers, especially when such treatments are necessary during the nectar flow. PMID:18459386

  8. Double proton transfer behavior and one-electron oxidation effect in double H-bonded glycinamide-formic acid complex.

    PubMed

    Li, Ping; Bu, Yuxiang

    2004-11-22

    The behavior of double proton transfer occurring in a representative glycinamide-formic acid complex has been investigated at the B3LYP/6-311 + + G( * *) level of theory. Thermodynamic and, especially, kinetic parameters, such as tautomeric energy, equilibrium constant, and barrier heights have been discussed, respectively. The relevant quantities involved in the double proton transfer process, such as geometrical changes, interaction energies, and intrinsic reaction coordinate calculations have also been studied. Computational results show that the participation of a formic acid molecule favors the proceeding of the proton transfer for glycinamide compared with that without mediate-assisted case. The double proton transfer process proceeds with a concerted mechanism rather than a stepwise one since no ion-pair complexes have been located during the proton transfer process. The calculated barrier heights are 11.48 and 0.85 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 2.95 and 2.61 kcal/mol to 8.53 and -1.76 kcal/mol if further inclusion of zero-point vibrational energy corrections, where the negative barrier height implies that the reverse reaction should proceed with barrierless spontaneously, analogous to that occurring between glycinamide and formamide. Furthermore, solvent effects on the thermodynamic and kinetic processes have also been predicted qualitatively employing the isodensity surface polarized continuum model within the framework of the self-consistent reaction field theory. Additionally, the oxidation process for the double H-bonded glycinamide-formic acid complex has also been investigated. Contrary to that neutral form possessing a pair of two parallel intermolecular H bonds, only a single H bond with a comparable strength has been found in its ionized form. The vertical and adiabatic ionization potentials for the neutral complex have been determined to be about 9.40 and 8.69 e

  9. Reexamination of CO formation during formic acid decomposition on the Pt(1 1 1) surface in the gas phase

    NASA Astrophysics Data System (ADS)

    Wang, Yingying; Zhang, Dongju; Liu, Peng; Liu, Chengbu

    2016-08-01

    Existing theoretical results for formic acid (HCOOH) decomposition on Pt(1 1 1) cannot rationalize the easy CO poisoning of the catalysts in the gas phase. The present work reexamined HCOOH decomposition on Pt(1 1 1) by considering the effect of the initial adsorption structure of the reactant on the reactivity. Our calculations present a new adsorption configuration of HCOOH on Pt(1 1 1), from which the formation of CO is found to be competing with the formation of CO2. The newly proposed mechanism improves our understanding for the mechanism of HCOOH decomposition catalyzed by Pt-based catalysts.

  10. Trifluoroethanol-containing RP-HPLC mobile phases for the separation of transmembrane peptides human glycophorin-A, integrin alpha-1, and p24: analysis and prevention of potential side reactions due to formic acid.

    PubMed

    Hara, Toshiaki; Huang, Yue; Ito, Akihiro; Kawakami, Toru; Hojo, Hironobu; Murata, Michio

    2015-02-01

    Reversed-phase high-pressure liquid chromatography analysis and purification of three hydrophobic, aggregation-prone peptides, composed mainly of the transmembrane (TM) sequence, were performed using elution systems containing 2,2,2-trifluoroethanol (TFE). The addition of 10-16% TFE to a common mobile phase, such as a water/acetonitrile/propanol (PrOH) or a water/PrOH/formic acid system, markedly improved the chromatographic separation of these peptides. The superior performance of TFE-containing systems in separating peptides over water/PrOH/formic acid systems [Bollhagen R. et al., J. Chromatogr. A, 1995; 711: 181-186.] clearly demonstrated that adding TFE to the mobile phase is one of best methods for TM-peptide purification. Characterization of the potential side reactions using MALDI and ESI-LIT/Orbitrap mass spectrometry indicated that prolonged incubation of peptides in a mixture of TFE-formic acid possibly induces O-formylation of the Ser residue and N-formylation of the N-terminus of peptides. The conditions for selective removal of the formyl groups from TM peptides were also screened. We believe that these results will expand our ability to analyze and prepare hydrophobic, aggregation-prone TM peptides and proteins. PMID:25504594

  11. Formic acid enhanced effective degradation of methyl orange dye in aqueous solutions under UV-Vis irradiation.

    PubMed

    Wang, Jingjing; Bai, Renbi

    2016-09-15

    Developing efficient technologies to treat recalcitrant organic dye wastewater has long been of great research and practical interest. In this study, a small molecule, formic acid (FA), was applied as a process enhancer for the degradation of methyl orange (MO) dye as a model recalcitrant organic pollutant in aqueous solutions under the condition of UV-Vis light irradiation and air aeration at the ambient temperature of 25 °C. It was found that the decolouration of the dye solutions can be rapidly achieved, reducing the time, for example, from around 17.6 h without FA to mostly about less than 2 h with the presence of FA. The mineralization rate of MO dye reached as high as 81.8% in 1.5 h in the case of initial MO dye concentration at 25 mg L(-1), which is in contrast to nearly no mineralization of the MO dye for a similar system without the FA added. The study revealed that the generation of the H2O2 species in the system was enhanced and the produced OH radicals effectively contributed to the degradation of the MO dye. Process parameters such as the initial concentration of MO dye, FA dosage and solution pH were all found to have some effect on the degradation efficiency under the same condition of UV-Vis light irradiation and air aeration. The MO dye degradation performance was found to follow a first-order reaction rate to the MO dye concentration in most cases and there existed a positive correlation between the reaction rate constant and the initial FA concentration. Compared to the traditional H2O2/UV-Vis oxidation system, the use of FA as a process-enhancing agent can have the advantages of low cost, easy availability, and safe to use. The study hence demonstrates a promising approach to use a readily available small molecule of FA to enhance the degradation of recalcitrant organic pollutants, such as MO dye, especially for their pre-treatment. PMID:27258621

  12. Electrodeposited platinum thin films with preferential (100) orientation: Characterization and electrocatalytic properties for ammonia and formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Bertin, Erwan; Garbarino, Sébastien; Guay, Daniel; Solla-Gullón, José; Vidal-Iglesias, Francisco J.; Feliu, Juan M.

    2013-03-01

    The electrocatalytic activity of preferentially oriented {100} Pt electrodes for the electro-oxidation of ammonia (0.2 M NaOH + 0.1 M NH3) and formic acid (0.5 M HCOOH + 0.5 M H2SO4) was assessed. They were prepared without using any surfactant through potentiostatic deposition (Ed = -0.10 V vs RHE, [HCl] = 10 mM and [Na2PtCl6·6H2O] = 0.5 mM) and by varying the deposition charge. For comparison, polycrystalline Pt thin films were prepared using the same solution but with Ed = +0.10 V vs RHE. Quantification of the fraction of (111) and (100) sites was performed by bismuth irreversible adsorption and deconvolution of the hydrogen region, respectively. Samples with as much as 47% of (100) surface sites were obtained. The preferential orientation was further confirmed by CO stripping voltammetry that exhibits similar characteristic features, as well as a similar potential of zero total charge than those expected for a preferential (100) surface. As compared to polycrystalline Pt, the occurrence of Pt (100) surface sites leads to an electrocatalytic activity enhancement by a factor of 4.8 and 2.6 (expressed as μA cmPt-2) for the oxidation of ammonia and formic acid, respectively.

  13. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights.

    PubMed

    Mellmann, Dörthe; Barsch, Enrico; Bauer, Matthias; Grabow, Kathleen; Boddien, Albert; Kammer, Anja; Sponholz, Peter; Bentrup, Ursula; Jackstell, Ralf; Junge, Henrik; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2014-10-13

    The iron-catalyzed dehydrogenation of formic acid has been studied both experimentally and mechanistically. The most active catalysts were generated in situ from cationic Fe(II) /Fe(III) precursors and tris[2-(diphenylphosphino)ethyl]phosphine (1, PP3 ). In contrast to most known noble-metal catalysts used for this transformation, no additional base was necessary. The activity of the iron catalyst depended highly on the solvent used, the presence of halide ions, the water content, and the ligand-to-metal ratio. The optimal catalytic performance was achieved by using [FeH(PP3 )]BF4 /PP3 in propylene carbonate in the presence of traces of water. With the exception of fluoride, the presence of halide ions in solution inhibited the catalytic activity. IR, Raman, UV/Vis, and EXAFS/XANES analyses gave detailed insights into the mechanism of hydrogen generation from formic acid at low temperature, supported by DFT calculations. In situ transmission FTIR measurements revealed the formation of an active iron formate species by the band observed at 1543 cm(-1) , which could be correlated with the evolution of gas. This active species was deactivated in the presence of chloride ions due to the formation of a chloro species (UV/Vis, Raman, IR, and XAS). In addition, XAS measurements demonstrated the importance of the solvent for the coordination of the PP3 ligand. PMID:25196789

  14. Conversion of hemicellulose sugars catalyzed by formic acid: kinetics of the dehydration of D-xylose, L-arabinose, and D-glucose.

    PubMed

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2015-04-24

    The pre-treatment of lignocellulosic biomass produces a liquid stream of hemicellulose-based sugars, which can be further converted to high-value chemicals. Formosolv pulping and the Milox process use formic acid as the fractionating agent, which can be used as the catalyst for the valorisation of hemicellulose sugars to platform chemicals. The objective of this study was to investigate the reaction kinetics of major components in the hemicelluloses fraction of biomass, that is, D-xylose, L-arabinose and D-glucose. The kinetics experiments for each sugar were performed at temperatures between 130 and 170 °C in various formic acid concentrations (10-64 wt %). The implications of these kinetic models on the selectivity of each sugar to the desired products are discussed. The models were used to predict the reaction kinetics of solutions that resemble the liquid stream obtained from the fractionation process of biomass using formic acid. PMID:25821128

  15. Formic acid treatment for control of Varroa destructor (Mesostigmata: Varroidae) and safety to Apis mellifera (Hymenoptera: Apidae) under southern United States conditions.

    PubMed

    Elzen, Patti J; Westervelt, David; Lucas, Raymond

    2004-10-01

    The efficacy of a formic acid pad formulation was field tested for control of the honey bee parasitic mite Varroa destructor Anderson & Trueman in Florida and Texas. This pad formulation gave 39.8 +/- 11.1% control at the end of a 6-wk treatment period, which did not significantly differ from the initial sample date. Coumaphos treatment provided poor control (38.4 +/- 11.1%) over the 6-wk period, confirming reports of coumaphos resistance in the region. Under relatively warm winter conditions in southern Texas, formic acid caused mortality of developing eggs and brood. If resistance by V. destructor to the two acaricides registered for its control in the United States continues, the formic acid pad could provide an alternative compound to use as part of an integrated pest management approach. Given the low control seen in this trial, however, modifications of application technology would seem necessary. PMID:15568336

  16. On the gas-particle partitioning of soluble organic aerosol in two urban atmospheres with contrasting emissions: 2. Gas and particle phase formic acid

    NASA Astrophysics Data System (ADS)

    Liu, Jiumeng; Zhang, Xiaolu; Parker, Eric T.; Veres, Patrick R.; Roberts, James M.; de Gouw, Joost A.; Hayes, Patrick L.; Jimenez, Jose L.; Murphy, Jennifer G.; Ellis, Raluca A.; Huey, L. Greg; Weber, Rodney J.

    2012-10-01

    Gas and fine particle (PM2.5) phase formic acid concentrations were measured with online instrumentation during separate one-month studies in the summer of 2010 in Los Angeles (LA), CA, and Atlanta, GA. In both urban environments, median gas phase concentrations were on the order of a few ppbv (LA 1.6 ppbv, Atlanta 2.3 ppbv) and median particle phase concentrations were approximately tens of ng/m3 (LA 49 ng/m3, Atlanta 39 ng/m3). LA formic acid gas and particle concentrations had consistent temporal patterns; both peaked in the early afternoon and generally followed the trends in photochemical secondary gases. Atlanta diurnal trends were more irregular, but the mean diurnal profile had similar afternoon peaks in both gas and particle concentrations, suggesting a photochemical source in both cities. LA formic acid particle/gas (p/g) ratios ranged between 0.01 and 12%, with a median of 1.3%. No clear evidence that LA formic acid preferentially partitioned to particle water was observed, except on three overcast periods of suppressed photochemical activity. Application of Henry's Law to predict partitioning during these periods greatly under-predicted particle phase formate concentrations based on bulk aerosol liquid water content (LWC) and pH estimated from thermodynamic models. In contrast to LA, formic acid partitioning in Atlanta appeared to be more consistently associated with elevated relative humidity (i.e., aerosol LWC), although p/g ratios were somewhat lower, ranging from 0.20 to 5.8%, with a median of 0.8%. Differences in formic acid gas absorbing phase preferences between these two cities are consistent with that of bulk water-soluble organic carbon reported in a companion paper.

  17. On the gas-particle partitioning of soluble organic aerosol in two urban atmospheres with contrasting emissions: 2. Gas and particle phase formic acid

    NASA Astrophysics Data System (ADS)

    Liu, Jiumeng; Zhang, Xiaolu; Parker, Eric T.; Veres, Patrick R.; Roberts, James M.; Gouw, Joost A.; Hayes, Patrick L.; Jimenez, Jose L.; Murphy, Jennifer G.; Ellis, Raluca A.; Huey, L. Greg; Weber, Rodney J.

    2011-11-01

    Gas and fine particle (PM2.5) phase formic acid concentrations were measured with online instrumentation during separate one-month studies in the summer of 2010 in Los Angeles (LA), CA, and Atlanta, GA. In both urban environments, median gas phase concentrations were on the order of a few ppbv (LA 1.6 ppbv, Atlanta 2.3 ppbv) and median particle phase concentrations were approximately tens of ng/m3 (LA 49 ng/m3, Atlanta 39 ng/m3). LA formic acid gas and particle concentrations had consistent temporal patterns; both peaked in the early afternoon and generally followed the trends in photochemical secondary gases. Atlanta diurnal trends were more irregular, but the mean diurnal profile had similar afternoon peaks in both gas and particle concentrations, suggesting a photochemical source in both cities. LA formic acid particle/gas (p/g) ratios ranged between 0.01 and 12%, with a median of 1.3%. No clear evidence that LA formic acid preferentially partitioned to particle water was observed, except on three overcast periods of suppressed photochemical activity. Application of Henry's Law to predict partitioning during these periods greatly under-predicted particle phase formate concentrations based on bulk aerosol liquid water content (LWC) and pH estimated from thermodynamic models. In contrast to LA, formic acid partitioning in Atlanta appeared to be more consistently associated with elevated relative humidity (i.e., aerosol LWC), although p/g ratios were somewhat lower, ranging from 0.20 to 5.8%, with a median of 0.8%. Differences in formic acid gas absorbing phase preferences between these two cities are consistent with that of bulk water-soluble organic carbon reported in a companion paper.

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

    DOEpatents

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

    2015-08-04

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

  19. Enhanced electroactivity of Pd nanocrystals supported on H3PMo12O40/carbon for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Zhao, Xiao; Zhu, Jianbing; Liang, Liang; Liu, Changpeng; Liao, Jianhui; Xing, Wei

    2012-07-01

    The preparation of highly dispersed precious metal catalysts is an important subject for fuel cell applications. Here, using a phosphomolybdic acid (PMo12)-assisted method, a Pd-PMo12/C catalyst with uniform Pd nanoparticles is prepared. The TEM results show that the presence of PMo12 facilitates the formation of uniform Pd particles with an average particle size of 3.2 nm. More importantly, the Pd-PMo12/C catalyst displays an enhanced activity and stability for formic acid electro-oxidation and a better tolerance toward CO poisoning than Pd nanocatalysts prepared with sodium citrate as a stabilizer. A combination of the composition and structure analyses show that the reasons for the improved electro-catalytic activity of the Pd-PMo12/C catalyst involve the metal-support interaction, the richer Pd oxide/hydrous oxide content and the inherent properties of PMo12.

  20. Preparation of AuPt alloy foam films and their superior electrocatalytic activity for the oxidation of formic acid.

    PubMed

    Liu, Jun; Cao, Ling; Huang, Wei; Li, Zelin

    2011-09-01

    AuPt alloy films with three-dimensional (3D) hierarchical pores consisting of interconnected dendrite walls were successfully fabricated by a strategy of cathodic codeposition utilizing the hydrogen bubble dynamic template. The foam films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Due to the special porous structure, the electronic property, and the assembly effect, the AuPt alloy foam films show superior electrocatalytic activity toward the electrooxidation of formic acid in acidic solution, and the prepared 3D porous AuPt alloy films also show high activity and long stability for the electrocatalytic oxidation of methanol, where synergistic effect plays an important role in addition to the electronic effect and assembly effect. These findings provide more insights into the AuPt bimetallic nanomaterials for electrocatalytic applications. PMID:21838240

  1. Nanoporous bimetallic Pt-Au alloy nanocomposites with superior catalytic activity towards electro-oxidation of methanol and formic acid.

    PubMed

    Zhang, Zhonghua; Wang, Yan; Wang, Xiaoguang

    2011-04-01

    We present a facile route to fabricate novel nanoporous bimetallic Pt-Au alloy nanocomposites by dealloying a rapidly solidified Al(75)Pt(15)Au(10) precursor under free corrosion conditions. The microstructure of the precursor and the as-dealloyed sample was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and energy dispersive X-ray (EDX) analysis. The Al(75)Pt(15)Au(10) precursor is composed of a single-phase Al(2)(Au,Pt) intermetallic compound, and can be fully dealloyed in a 20 wt.% NaOH or 5 wt.% HCl aqueous solution. The dealloying leads to the formation of the nanoporous Pt(60)Au(40) nanocomposites (np-Pt(60)Au(40) NCs) with an fcc structure. The morphology, size and crystal orientation of grains in the precursor can be conserved in the resultant nanoporous alloy. The np-Pt(60)Au(40) NCs consist of two zones with distinct ligament/channel sizes and compositions. The formation mechanism of these np-Pt(60)Au(40) NCs can be rationalized based upon surface diffusion of more noble elements and spinodal decomposition during dealloying. Electrochemical measurements demonstrate that the np-Pt(60)Au(40) NCs show superior catalytic activity towards the electro-oxidation of methanol and formic acid in the acid media compared to the commercial JM-Pt/C catalyst. This material can find potential applications in catalysis related areas, such as direct methanol or formic acid fuel cells. Our findings demonstrate that dealloying is an effective and simple strategy to realize the alloying of immiscible systems under mild conditions, and to fabricate novel nanostructures with superior performance. PMID:21311802

  2. Complementary cavity-enhanced spectrometers to investigate the OH + CH combination band in trans-formic acid.

    PubMed

    Golebiowski, D; Földes, T; Vanfleteren, T; Herman, M; Perrin, A

    2015-07-01

    We have used continuous-wave cavity ring-down and femto-Fourier transform-cavity-enhanced absorption spectrometers to record the spectrum of the OH-stretching + CH-stretching (ν1 + ν2) combination band in trans-formic acid, with origin close to 6507 cm(-1). They, respectively, allowed resolving and simplifying the rotational structure of the band near its origin under jet-cooled conditions (Trot = 10 K) and highlighting the overview of the band under room temperature conditions. The stronger B-type and weaker A-type subbands close to the band origin could be assigned, as well as the main B-type Q branches. The high-resolution analysis was hindered by numerous, severe perturbations. Rotational constants are reported with, however, limited physical meaning. The ν1 + ν2 transition moment is estimated from relative intensities to be 24° away from the principal b-axis of inertia. PMID:26156476

  3. Synthesis of cubic and spherical Pd nanoparticles on graphene and their electrocatalytic performance in the oxidation of formic acid

    NASA Astrophysics Data System (ADS)

    Yang, Sudong; Shen, Chengmin; Tian, Yuan; Zhang, Xiaogang; Gao, Hong-Jun

    2014-10-01

    Single-crystal palladium nanoparticles (NPs) with controllable morphology were synthesized on the surface of reduced graphene oxide (RGO) by a novel procedure, namely reducing palladium acetylacetonate [Pd(acac)2] with the N-methylpyrrolidone (NMP) solvent in the presence of poly(vinylpyrrolidone) (PVP). The resulting Pd nanocrystals (8 nm in diameter) were uniformly distributed on the RGO. A possible formation mechanism is discussed. The electrocatalytic performance of Pd nanocrystal/RGO catalysts during formic acid oxidation was investigated, which revealed that the cubic Pd/RGO catalyst performed significantly better than the spherical Pd/RGO catalyst. The shape of Pd nanocrystals on the surface of graphene nanosheets can be easily controlled via tuning the synthesis parameters, resulting in tunable catalytic properties. Moreover, this method can be easily extended to fabricate other noble metal nanostructures.

  4. Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate

    NASA Technical Reports Server (NTRS)

    Jacob, D. J.

    1986-01-01

    The chemistry of OH in nonprecipitating tropospheric clouds was studied using a coupled gas phase/aqueous phase chemical model. The simulation takes into account the radial dependence of the concentrations of short lived aqueous phase species, in particular, O3(aq) OH(aq). Formic acid is shown to be rapidly produced by the aqueous phase reaction between H2C(OH)2 and OH, but HCOO(-) and OH, but HCOO(-) is in turn rapidly oxidized by OH(aq). The HCOOH concentration in cloud is shown to be strongly dependent on the pH of the cloud water; clouds with pH greater than 5 are not efficient HCOOH sources. A novel mechanism is proposed for the oxidation of S(IV) by OH(aq), with the main product predicted to be peroxymonosulfate, HSO5(-). The latter could contribute significantly to total cloud water sulfur.

  5. Synchronized Current Oscillations of Formic Acid Electro-oxidation in a Microchip-based Dual-Electrode Flow Cell

    PubMed Central

    Kiss, István Z.; Munjal, Neil; Martin, R. Scott

    2009-01-01

    We investigate the oscillatory electro-oxidation of formic acid on platinum in a microchip-based dual-electrode cell with microfluidic flow control. The main dynamical features of current oscillations on single Pt electrode that had been observed in macro-cells are reproduced in the microfabricated electrochemical cell. In dual-electrode configuration nearly in-phase synchronized current oscillations occur when the reference/counter electrodes are placed far away from the microelectrodes. The synchronization disappears with close reference/counter electrode placements. We show that the cause for synchronization is weak albeit important, bidirectional electrical coupling between the electrodes; therefore the unidirectional mass transfer interactions are negligible. The experimental design enables the investigation of the dynamical behavior in micro-electrode arrays with well-defined control of flow of the electrolyte in a manner where the size and spacing of the electrodes can be easily varied. PMID:20160883

  6. Dehydrogenation of Formic Acid at Room Temperature: Boosting Palladium Nanoparticle Efficiency by Coupling with Pyridinic-Nitrogen-Doped Carbon.

    PubMed

    Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei; He, He-Yong; Huang, Fu-Qiang; Cao, Yong

    2016-09-19

    The use of formic acid (FA) to produce molecular H2 is a promising means of efficient energy storage in a fuel-cell-based hydrogen economy. To date, there has been a lack of heterogeneous catalyst systems that are sufficiently active, selective, and stable for clean H2 production by FA decomposition at room temperature. For the first time, we report that flexible pyridinic-N-doped carbon hybrids as support materials can significantly boost the efficiency of palladium nanoparticle for H2 generation; this is due to prominent surface electronic modulation. Under mild conditions, the optimized engineered Pd/CN0.25 catalyst exhibited high performance in both FA dehydrogenation (achieving almost full conversion, and a turnover frequency of 5530 h(-1) at 25 °C) and the reversible process of CO2 hydrogenation into FA. This system can lead to a full carbon-neutral energy cycle. PMID:27552650

  7. Morphological features of electrodeposited Pt nanoparticles and its application as anode catalysts in polymer electrolyte formic acid fuel cells

    NASA Astrophysics Data System (ADS)

    Jeon, Hongrae; Joo, Jiyong; Kwon, Youngkook; Uhm, Sunghyun; Lee, Jaeyoung

    Electrodeposited Pt nanoparticles on carbon substrate show various morphologies depending on the applied potentials. Dendritic, pyramidal, cauliflower-like, and hemi-spherical morphologies of Pt are formed at potential ranges between -0.2 and 0.3 V (vs. Ag/AgCl) and its particle sizes are distributed from 8 to 26 nm. Dendritic bulky particles over 20 nm are formed at an applied potential of -0.2 V, while low deposition potential of 0.2 V causes dense hemi-spherical structure of Pt less than 10 nm. The influence of different Pt shapes on an electrocatalytic oxidation of formic acid is represented. Consequently, homogeneous distribution of Pt nanoparticles with average particle of ca. 14 nm on carbon paper results in a high surface to volume ratio and the better power performance in a fuel cell application.

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

    PubMed

    Yang, Sudong; Shen, Chengmin; Liang, Yanyu; Tong, Hao; He, Wei; Shi, Xuezhao; Zhang, Xiaogang; Gao, Hong-jun

    2011-08-01

    A novel electrode material based on graphene oxide (GO)-polypyrrole (PPy) composites was synthesized by in situ chemical oxidation polymerization. Palladium nanoparticles (NPs) with a diameter of 4.0 nm were loaded on the reduced graphene oxide(RGO)-PPy composites by a microwave-assisted polyol process. Microstructure analysis showed that a layer of coated PPy film with monodisperse Pd NPs is present on the RGO surface. The Pd/RGO-PPy catalysts exhibit excellent catalytic activity and stability for formic acid electro-oxidation when the weight feed ratio of GO to pyrrole monomer is 2:1. The superior performance of Pd/RGO-PPy catalysts may arise from utilization of heterogeneous nucleation sites for NPs and the greatly increased electronic conductivity of the supports. PMID:21713273

  9. Polyhedral Palladium–Silver Alloy Nanocrystals as Highly Active and Stable Electrocatalysts for the Formic Acid Oxidation Reaction

    PubMed Central

    Fu, Geng-Tao; Liu, Chang; Zhang, Qi; Chen, Yu; Tang, Ya-Wen

    2015-01-01

    Polyhedral noble–metal nanocrystals have received much attention and wide applications as electrical and optical devices as well as catalysts. In this work, a straightforward and effective hydrothermal route for the controllable synthesis of the high-quality Pd–Ag alloy polyhedrons with uniform size is presented. The morphology, composition and structure of the Pd–Ag alloy polyhedrons are fully characterized by the various physical techniques, demonstrating the Pd–Ag alloy polyhedrons are highly alloying. The formation/growth mechanisms of the Pd–Ag alloy polyhedrons are explored and discussed based on the experimental observations and discussions. As a preliminary electrochemical application, the Pd–Ag alloy polyhedrons are applied in the formic acid oxidation reaction, which shows higher electrocatalytic activity and stability than commercially available Pd black due to the “synergistic effects” between Pd and Ag atoms. PMID:26329555

  10. FORMATION OF CARBON DIOXIDE, METHANOL, ETHANOL, AND FORMIC ACID ON AN ICY GRAIN ANALOG USING FAST OXYGEN ATOMS

    SciTech Connect

    Madzunkov, S. M.; MacAskill, J. A.; Chutjian, A.

    2010-03-20

    Carbon dioxide (CO{sub 2}), methanol (CH{sub 3}OH), ethanol (CH{sub 3}CH{sub 2}OH), and formic acid (HCOOH) have been formed in collisions of a superthermal, 9 eV beam of O({sup 3} P) atoms with CH{sub 4} molecules, with an over coat of CO molecules, adsorbed on a gold surface at 4.8 K. The products are detected using temperature programmed-desorption and quadrupole mass spectrometry. Identification of the species is carried out through use of the Metropolis random walk algorithm as constrained by the fractionation patterns of the detected species. Relative formation yields are reported and reaction sequences are given to account for possible formation routes.

  11. Preparation of Nanoporous Pd by Dealloying Al-Pd Slice and Its Electrocatalysts for Formic Acid Oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Nana; Wang, Tianning; Nie, Chen; Sun, Lanju; Li, Jie; Geng, Haoran

    2016-01-01

    AlPd alloy slices with a thickness of 0.5 mm were taken as precursors during the fabrication of nanoporous palladium (np-Pd) using chemical dealloying in NaOH solution or electrochemical dealloying in NaCl solution. Scanning electron microscope photos and x-ray diffraction patterns demonstrate a full dealloying of Al out of the precursors and the formation of nP-Pd which is characterized by a three-dimensional, bicontinuous, ligament-channel structure with nanoscale length scales. Electrochemical measurements were performed to evaluate the electrocatalytic activity and structure stability of np-Pd towards formic acid oxidation and it showed a good structure stability.

  12. The Melting Curve and High-Pressure Chemistry of Formic Acid to 8 GPa and 600 K

    SciTech Connect

    Montgomery, W; Zaug, J M; Howard, W M; Goncharov, A F; Crowhurst, J C; Jeanloz, R

    2005-04-13

    We have determined the melting temperature of formic acid (HCOOH) to 8.5 GPa using infrared absorption spectroscopy, Raman spectroscopy and visual observation of samples in a resistively heated diamond-anvil cell. The experimentally determined melting curve compares favorably with a two-phase thermodynamic model. Decomposition reactions were observed above the melting temperature up to a pressure of 6.5 GPa, where principal products were CO{sub 2}, H{sub 2}O and CO. At pressures above 6.5 GPa, decomposition led to solid-like reaction products. Infrared and Raman spectra of these recovered products indicate that pressure affects the nature of carbon-carbon bonding.

  13. Polyhedral Palladium-Silver Alloy Nanocrystals as Highly Active and Stable Electrocatalysts for the Formic Acid Oxidation Reaction

    NASA Astrophysics Data System (ADS)

    Fu, Geng-Tao; Liu, Chang; Zhang, Qi; Chen, Yu; Tang, Ya-Wen

    2015-09-01

    Polyhedral noble-metal nanocrystals have received much attention and wide applications as electrical and optical devices as well as catalysts. In this work, a straightforward and effective hydrothermal route for the controllable synthesis of the high-quality Pd-Ag alloy polyhedrons with uniform size is presented. The morphology, composition and structure of the Pd-Ag alloy polyhedrons are fully characterized by the various physical techniques, demonstrating the Pd-Ag alloy polyhedrons are highly alloying. The formation/growth mechanisms of the Pd-Ag alloy polyhedrons are explored and discussed based on the experimental observations and discussions. As a preliminary electrochemical application, the Pd-Ag alloy polyhedrons are applied in the formic acid oxidation reaction, which shows higher electrocatalytic activity and stability than commercially available Pd black due to the “synergistic effects” between Pd and Ag atoms.

  14. A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects

    SciTech Connect

    Choi, Sang; Herron, Jeffrey A.; Scaranto, Jessica; Huang, Hongwen; Wang, Yi; Xia, Xiaohu; Lv, Tian; Park, Jinho; Peng, Hsin-Chieh; Mavrikakis, Manos; Xia, Younan

    2015-07-13

    Palladium has been recognized as the best anodic, monometallic electrocatalyst for the formic acid oxidation (FAO) reaction in a direct formic acid fuel cell. Here we report a systematic study of FAO on a variety of Pd nanocrystals, including cubes, right bipyramids, octahedra, tetrahedra, decahedra, and icosahedra. These nanocrystals were synthesized with approximately the same size, but different types of facets and twin defects on their surfaces. Our measurements indicate that the Pd nanocrystals enclosed by {1 0 0} facets have higher specific activities than those enclosed by {1 1 1} facets, in agreement with prior observations for Pd single-crystal substrates. If comparing nanocrystals predominantly enclosed by a specific type of facet, {1 0 0} or {1 1 1}, those with twin defects displayed greatly enhanced FAO activities compared to their single-crystal counterparts. To rationalize these experimental results, we performed periodic, self-consistent DFT calculations on model single-crystal substrates of Pd, representing the active sites present in the nanocrystals used in the experiments. The calculation results suggest that the enhancement of FAO activity on defect regions, represented by Pd(2 1 1) sites, compared to the activity of both Pd(1 0 0) and Pd(1 1 1) surfaces, could be attributed to an increased flux through the HCOO-mediated pathway rather than the COOH-mediated pathway on Pd(2 1 1). Since COOH has been identified as a precursor to CO, a site-poisoning species, a lower coverage of CO at the defect regions will lead to a higher activity for the corresponding nanocrystal catalysts, containing those defect regions.

  15. Tropospheric Emission Spectrometer (TES) satellite observations of ammonia, methanol, formic acid, and carbon monoxide over the Canadian oil sands: validation and model evaluation

    EPA Science Inventory

    The wealth of air quality information provided by satellite infrared observations of ammonia (NH3), carbon monoxide (CO), formic acid (HCOOH), and methanol (CH3OH) is currently being explored and used for a number of applications, especially at regional or global scales. These ap...

  16. Efficacy of formic acid in gel for Varroa control in Apis mellifera L.: importance of the dispenser position inside the hive.

    PubMed

    Eguaras, Martin; Palacio, Maria Alejandra; Faverin, Claudia; Basualdo, Marina; Del Hoyo, Marcelo Luis; Velis, Gustavo; Bedascarrasbure, Enrique

    2003-02-13

    The efficacy of formic acid in a gel matrix was evaluated in two groups of honeybee colonies. In Group 1, a dispenser with 120 g of formic acid (70%) in gel was placed on the brood combs and another dispenser with the same dose was located on the hive bottom (total dose, 240 g). Group 2 received two doses of 240 g of formic acid (70%) in gel and each application was applied in two dispensers containing 120 g of the formic acid solution each and they were located over the brood chamber (total dose, 480 g). In Group 2, the period between both applications was 15 days, and the efficacies after the first and both applications were calculated. Significant differences were registered for final efficacy between both groups. When final efficacy of Group 1 was compared with efficacy after first application of Group 2, significant differences were found (P=0.0005). Same doses in different positions within the hive have different final efficacy. The higher efficacy was registered when the dispensers were placed over brood combs and on the hive bottom. It is suggested that efficacy is related to dispenser position within the hive. PMID:12531298

  17. Conversion of Saccharides into Formic Acid using Hydrogen Peroxide and a Recyclable Palladium(II) Catalyst in Aqueous Alkaline Media at Ambient Temperatures

    PubMed Central

    Zargari, N.; Kim, Y.; Jung, K. W.

    2015-01-01

    We have developed an effective method that converts a variety of mono- and disaccharides into formic acid predominantly. Our recyclable NHC-amidate palladium(II) catalyst facilitated oxidative degradation of carbohydrates without using excess oxidant. Stoichiometric amounts of hydrogen peroxide and sodium hydroxide were employed at ambient temperatures. PMID:26421000

  18. Ultrafast synthesis of flower-like ordered Pd3Pb nanocrystals with superior electrocatalytic activities towards oxidation of formic acid and ethanol

    NASA Astrophysics Data System (ADS)

    Jana, Rajkumar; Subbarao, Udumula; Peter, Sebastian C.

    2016-01-01

    Ordered intermetallic nanocrystals with high surface area are highly promising as efficient catalysts for fuel cell applications because of their unique electrocatalytic properties. The present work discusses about the controlled synthesis of ordered intermetallic Pd3Pb nanocrystals in different morphologies at relatively low temperature for the first time by polyol and hydrothermal methods both in presence and absence of surfactant. Here for the first time we report surfactant free synthesis of ordered flower-like intermetallic Pd3Pb nanocrystals in 10 s. The structural characteristics of the nanocrystals are confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. The as synthesized ordered Pd3Pb nanocrystals exhibit far superior electrocatalytic activity and durability towards formic acid and ethanol oxidation over commercially available Pd black (Pd/C). The morphological variation of nanocrystals plays a crucial role in the electrocatalytic oxidation of formic acid and ethanol. Among the catalysts, the flower-like Pd3Pb shows enhanced activity and stability in electrocatalytic formic acid and ethanol oxidation. The current density and mass activity of flower-like Pd3Pb catalyst are higher by 2.5 and 2.4 times than that of Pd/C for the formic acid oxidation and 1.5 times each for ethanol oxidation.

  19. Structure-dependent photocatalytic decomposition of formic acid on the anatase TiO2(101) surface and strategies to increase its reaction rate

    NASA Astrophysics Data System (ADS)

    Ji, Yongfei; Luo, Yi

    2016-02-01

    Formic acid is a typical molecule that is involved in a lot important solar energy conversion processes. We perform first-principles calculations on the molecular mechanism of its photocatalytic decomposition reaction (PCD) on the anatase TiO2(101) surface. We find that the reaction barrier is sensitively dependent on the adsorption structure of the molecule. The one-step PCD of the monodentate formic acid has a lower barrier than that of bidentate formate. Coadsorbed water molecules can transform the formate from a bidentate to a monodentate configuration which greatly lower its decomposition barrier. Water molecule can also induce the spontaneous dissociation of the formic acid molecule. The monodentate dissociated formic acid is stabilized by the hydrogen bonds which will slightly enhance the barrier for its photodecomposition. However, the reaction rate can be further enhanced if the hydrogens are removed (for example, by oxygen molecules). Therefore, using coadsorbate and deliberately introducing and removing hydrogen bonds can be two strategies to tailor the photoreaction rate of the molecules.

  20. Facile one-pot surfactant-free synthesis of uniform Pd6Co nanocrystals on 3D graphene as an efficient electrocatalyst toward formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Lian Ying; Zhao, Zhi Liang; Yuan, Weiyong; Li, Chang Ming

    2016-01-01

    Ultrasmall and uniform Pd6Co nanocrystals were deposited on 3D graphene by a facile one-pot surfactant-free route for a catalyst toward formic acid oxidation, showing a much higher electrocatalytic activity, larger peak current density and better stability than Pd/3DG, Pd/C as well as commercial Pd-C, and thus offering great potential for an efficient anode catalyst toward high performance direct formic acid fuel cells.Ultrasmall and uniform Pd6Co nanocrystals were deposited on 3D graphene by a facile one-pot surfactant-free route for a catalyst toward formic acid oxidation, showing a much higher electrocatalytic activity, larger peak current density and better stability than Pd/3DG, Pd/C as well as commercial Pd-C, and thus offering great potential for an efficient anode catalyst toward high performance direct formic acid fuel cells. Electronic supplementary information (ESI) available: Experimental section and supplementary figures. See DOI: 10.1039/c5nr08512h

  1. A Convenient Palladium-Catalyzed Carbonylative Synthesis of Benzofuran-2(3 H)-ones with Formic Acid as the CO Source.

    PubMed

    Qi, Xinxin; Li, Hao-Peng; Wu, Xiao-Feng

    2016-09-01

    A general and convenient palladium-catalyzed carbonylation procedure for the synthesis of benzofuran-2(3 H)-ones from phenols and aldehydes has been developed. With formic acid as the CO source, a variety of benzofuran-2(3 H)-ones were obtained in moderate to good yields. PMID:27539230

  2. Analytical continuation in coupling constant method; application to the calculation of resonance energies and widths for organic molecules: Glycine, alanine and valine and dimer of formic acid

    NASA Astrophysics Data System (ADS)

    Papp, P.; Matejčík, Š.; Mach, P.; Urban, J.; Paidarová, I.; Horáček, J.

    2013-06-01

    The method of analytic continuation in the coupling constant (ACCC) in combination with use of the statistical Padé approximation is applied to the determination of resonance energy and width of some amino acids and formic acid dimer. Standard quantum chemistry codes provide accurate data which can be used for analytic continuation in the coupling constant to obtain the resonance energy and width of organic molecules with a good accuracy. The obtained results are compared with the existing experimental ones.

  3. Impact of surface roughness of Au core in Au/Pd core-shell nanoparticles toward formic acid oxidation - Experiment and simulation

    NASA Astrophysics Data System (ADS)

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-12-01

    The Au/Pd core-shell nanoparticles (NPs) were synthesized via galvanic replacement of Cu by Pd on hollow Au cores by adding different concentrations of Na2SO3 solution. It was found that the higher concentration of Na2SO3 that was used, the rougher the Au nanospheres became. However, the rougher Au surface may cause more defects in the Pd layers and decrease the catalytic abilities. The Au/Pd NPs synthesized using 0 M Na2SO3 (denoted as 0 M-Au/Pd NPs) have the smoothest Pd surface and demonstrate higher formic acid oxidation (FAO) activity (0.714 mA cm-2, normalized to the surface area of Pd) than other Au/Pd NPs and commercial Pd black (0.47 mA cm-2). Additional electrochemical characterization of the 0 M-Au/Pd NPs also demonstrated lower CO-stripping onset and peak potentials, higher stability (8× improvement in stabilized oxidation current), and superior durability (by 1.6×) than the Pd black. In addition, a simple simulation of FAO was adopted to predict the anodic curve by including reaction intermediates of formate and hydroxyl. The 0 M-Au/Pd NPs were found to show higher formate and lower hydroxyl coverage than the Pd black.

  4. Kinetic and equilibrium study on formic acid decomposition in relation to the water-gas-shift reaction.

    PubMed

    Yasaka, Yoshiro; Yoshida, Ken; Wakai, Chihiro; Matubayasi, Nobuyuki; Nakahara, Masaru

    2006-09-28

    Kinetics and equilibrium are studied on the hydrothermal decarbonylation and decarboxylation of formic acid, the intermediate of the water-gas-shift (WGS) reaction, in hot water at temperatures of 170-330 degrees C, to understand and control the hydrothermal WGS reaction. (1)H and (13)C NMR spectroscopy is applied to analyze as a function of time the quenched reaction mixtures in both the liquid and gas phases. Only the decarbonylation is catalyzed by HCl, and the reaction is first-order with respect to both [H(+)] and [HCOOH]. Consequently, the reaction without HCl is first and a half (1.5) order due to the unsuppressed ionization of formic acid. The HCl-accelerated decarbonylation path can thus be separated in time from the decarboxylation. The rate and equilibrium constants for the decarbonylation are determined separately by using the Henry constant (gas solubility data) for carbon monoxide in hot water. The rate constant for the decarbonylation is 1.5 x 10(-5), 2.0 x 10(-4), 3.7 x 10(-3), and 6.3 x 10(-2) mol(-1) kg s(-1), respectively, at 170, 200, 240, and 280 degrees C on the liquid branch of the saturation curve. The Arrhenius plot of the decarbonylation is linear and gives the activation energy as 146 +/- 3 kJ mol(-1). The equilibrium constant K(CO) = [CO]/[HCOOH] is 0.15, 0.33, 0.80, and 4.2, respectively, at 170, 200, 240, and 280 degrees C. The van't Hoff plot results in the enthalpy change of DeltaH = 58 +/- 6 kJ mol(-1). The decarboxylation rate is also measured at 240-330 degrees C in both acidic and basic conditions. The rate is weakly dependent on the solution pH and is of the order of 10(-4) mol kg(-1) s(-1) at 330 degrees C. Furthermore, the equilibrium constant K(CO2) = [CO(2)][H(2)]/[HCOOH] is estimated to be 1.0 x10(2) mol kg(-1) at 330 degrees C. PMID:16986841

  5. Theoretical Modeling of Formic Acid (HCOOH), Formate (HCOO(-)), and Ammonia (NH(4)) Vibrational Spectra in Astrophysical Ices

    NASA Technical Reports Server (NTRS)

    Park, Jin-Young; Woon, David E.

    2006-01-01

    Ions embedded in icy grain mantles are thought to account for various observed infrared spectroscopic features, particularly in certain young stellar objects. The dissociation of formic acid (HCOOH) in astrophysical ices to form the formate ion (HCOO(-)) was modeled with density functional theory cluster calculations. Like isocyanic acid (HOCN), HCOOH was found to spontaneously deprotonate when sufficient water is present to stabilize charge transfer complexes. Both ammonia and water can serve as proton acceptors, yielding ammonium (NH4(+)) and hydronium (H3O(+)) counterions. Computed frequencies of weak infrared features produced by stretching and bending modes in both HCOO(-) and HCOOH were compared with experimental and astronomical data. Our results confirm laboratory assignments that a band at 1381 cm(exp -1) can be attributed to the CH bend in either HCOO(-) or HCOOH, but a band at 1349 cm(exp -1) corresponds to CO stretching in HCOO(-). Another feature at 1710 cm(exp -1) (5.85 m) can possibly be assigned to a CO stretching mode in HCOOH, as suggested by experiment, but the agreement is less satisfactory. In addition, we examine and analyze spectroscopic features associated with NH+4, both as a counterion to HCOO(-) or OCN(-) and in isolation, in order to compare with experimental and astronomical data in the 7 m region.

  6. Ultrasound-promoted cold vapor generation in the presence of formic acid for determination of mercury by atomic absorption spectrometry.

    PubMed

    Gil, Sandra; Lavilla, Isela; Bendicho, Carlos

    2006-09-01

    A new cold vapor technique within the context of green chemistry is described for determination of mercury in liquid samples following high-intensity ultrasonication. Volatile Hg evolved in a sonoreactor without the use of a chemical reducing agent is carried to a quartz cell kept at room temperature for measurement of the atomic absorption. The mechanism involved lies in the reduction of Hg(II) to Hg(0) by reducing gases formed upon sonication and subsequent volatilization of Hg(0) due to the degassing effect caused by the cavitation phenomenon. Addition of a low molecular weight organic acid such as formic acid favors the process, but vapor generation also occurs from Hg solutions in ultrapure water. The detection limit of Hg was 0.1 microg/L, and the repeatability, expressed as relative standard deviation, was 4.4% (peak height). Addition of small amounts of oxidizing substances such as the permanganate or dichromate anions completely suppressed the formation of Hg(0), which confirms the above mechanism. Effect of other factors such as ultrasound irradiation time, ultrasound amplitude, and the presence of concomitants are also investigated. Some complexing anions such as chloride favored the stabilization of Hg(II) in solution, hence causing an interference effect on the ultrasound-assisted reduction/volatilization process. PMID:16944910

  7. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid

    PubMed Central

    Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit

    2014-01-01

    Summary Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects. PMID:24605281

  8. Large-Scale Distributions of Tropospheric Nitric, Formic, and Acetic acids Over the Westerm Pacific Basin During Wintertime

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Dibb, J. E.; Lefer, B. L.; Scheuer, E. M.; Bradshaw, J. D.; Sandholm, S. T.; Smyth, S.; Blake, D. R.; Blake, N. J.; Sachse, G. W.; Collins, J. E.; Gregory, G. L.

    1997-01-01

    We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).

  9. Towards understanding the TiO2-mediated photoredox process of Cu(II)-formic acid solution.

    PubMed

    He, Chun; Xiong, Ya; An, Taicheng; Zhu, Xihai

    2003-05-01

    The performance of TiO2-film was investigated in the process of simultaneous photocatalytic Cu(II) reduction and COD (chemical oxygen demand) removal from Cu(II)-containing formic acid solution during successive batch runs. It was found that, during the first batch run, the Cu(II) ions could increase the COD removal efficiency, synchronous to the Cu(0) deposition, however, decrease the efficiency by a factor of 22.5% with the continuative proceeding of the deposition for the second batch run. Unexpectedly, after the second run the COD removal efficiency remained a constant, ca. 40%, and no longer continued decrease. The unexpected observation was attributed to the cycle of Cu(II) deposition and Cu(0) re-dissolution due to air oxidation at pH 2.73. The attribution was primarily confirmed by the scanning electron microscope image and several fluctuation phenomena in the reaction process, such as pH, Cu(II) concentration and photocurrent. PMID:12744444

  10. Acrylonitrile-contamination induced enhancement of formic acid electro-oxidation at platinum nanoparticles modified glassy carbon electrodes

    NASA Astrophysics Data System (ADS)

    El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Deab, Mohamed S.; Ohsaka, Takeo; El-Anadouli, Bahgat E.

    2014-11-01

    Minute amount (∼1 ppm) of acrylonitrile (AcN), a possible contaminant, shows an unexpected enhancement for the direct electro-oxidation of formic acid (FAO) at Pt nanoparticles modified GC (nano-Pt/GC) electrodes. This is reflected by a remarkable increase of the current intensity of the direct oxidation peak (Ipd, at ca. 0.3 V) in the presence of AcN, concurrently with a significant decrease of the second (indirect) oxidation current (Ipind, at ca. 0.7 V), compared to that observed in the absence of AcN (i.e., at the unpoisoned Pt electrode). The extent of enhancement depends on the surface coverage (θ) of AcN at the surface of Pt nanoparticles. AcN is thought to favor the direct FAO by disturbing the contiguity of the Pt sites, which is necessary for CO adsorption. Furthermore, XPS measurements revealed a change in the electronic structure of Pt in presence of AcN, which has a favorable positive impact on the charge transfer during the direct FAO.

  11. Fabrication of Nitrogen-Doped Mesoporous-Carbon-Coated Palladium Nanoparticles: An Intriguing Electrocatalyst for Methanol and Formic Acid Oxidation.

    PubMed

    Ray, Chaiti; Dutta, Soumen; Sahoo, Ramkrishna; Roy, Anindita; Negishi, Yuichi; Pal, Tarasankar

    2016-05-20

    Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. PMID:27016895

  12. Nitrogen-doped carbon-TiO2 composite as support of Pd electrocatalyst for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Qin, Yuan-Hang; Li, Yunfeng; Lam, Thomas; Xing, Yangchuan

    2015-06-01

    We report Pd nanoparticles supported on a composite consisting of oxide TiO2 and nitrogen-doped carbon for formic acid oxidation (FAO). The nitrogen-doped carbon-TiO2 (NCx-TiO2) composite support was prepared by a simple polymerization-pyrolysis process using commercial TiO2 nanoparticles (P25). Surface analysis showed that elements of Ti, C, O, and N were present on the composite surface, on which nitrogen existed in both pyridinic and quaternary forms. Pd nanoparticles with a mean size of ca. 4 nm were uniformly deposited on the composite via a polyol process. Electrochemical characterizations showed that the NCx-TiO2-supported Pd particles (Pd/NCx-TiO2) exhibited an electrocatalytic activity towards FAO that almost doubled that of the carbon black-supported Pd particles (Pd/C) with much enhanced electrocatalytic stability. The better performance of the composite supported Pd was attributed to a possible electronic structure modification in the metallic Pd particles and bifunctional effect produced by the NCx-TiO2 composite.

  13. Highly efficient and autocatalytic H2O dissociation for CO2 reduction into formic acid with zinc

    NASA Astrophysics Data System (ADS)

    Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

    2014-03-01

    Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH- complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal.

  14. One-step electrochemical synthesis of preferentially oriented (111) Pd nanocrystals supported on graphene nanoplatelets for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Chen, Qing-Song; Xu, Zhong-Ning; Peng, Si-Yan; Chen, Yu-Min; Lv, Dong-Mei; Wang, Zhi-Qiao; Sun, Jing; Guo, Guo-Cong

    2015-05-01

    Pd nanocrystals supported on graphene nanoplatelets (Pd/GNP) have been successfully synthesized by simultaneously electrochemical milling of Pd wire and graphite rod. It should be stressed that without the assistance of graphite rod, the Pd nanocrystals are unable to be obtained individually from Pd wire under the same conditions. Investigations of SEM and TEM demonstrate that Pd/GNP are preferentially decorated with (111) faceted nanocrystals. XPS studies confirm the strong metal-support interaction in Pd/GNP and reveal the surface is almost composed of Pd(0) species. Electrochemical measurements show that the prepared Pd based catalyst exhibits superior electrocatalytic activity towards formic acid oxidation, which may be attributed to the combined effects involving the preferentially oriented (111) surface structure, specific electronic structure and high dispersion of Pd nanocrystals as well as the support effects of graphene nanoplatelets. The synthesis method is simple and effective to prepare excellent new carbon-supported electrocatalysts, which is of great significance for direct organic molecule fuel cell.

  15. Deciphering visible light photoreductive conversion of CO2 to formic acid and methanol using waste prepared material.

    PubMed

    Zhang, Qian; Lin, Cheng-Fang; Chen, Bor-Yann; Ouyang, Tong; Chang, Chang-Tang

    2015-02-17

    As gradual increases in atmospheric CO2 and depletion of fossil fuels have raised considerable public concern in recent decades, utilizing the unlimited solar energy to convert CO2 to fuels (e.g., formic acid and methanol) apparently could simultaneously resolve these issues for sustainable development. However, due to the complicated characteristics of CO2 reduction, the mechanism has yet to be disclosed. To clarify the postulated pathway as mentioned in the literature, the technique of electron paramagnetic resonance (ESR) was implemented herein to confirm the mechanism and related pathways of CO2 reduction under visible light using graphene-TiO2 as catalyst. The findings indicated that CO(-•) radicals, as the main intermediates, were first detected herein to react with several hydrogen ions and electrons for the formation of CH3OH. For example, the generation of CO(-•) radicals is possibly the vital rate-controlling step for conversion of CO2 to methanol as hypothesized elsewhere. The kinetics behind the proposed mechanism was also determined in this study. The mechanism and kinetics could provide the in-depth understanding to the pathway of CO2 reduction and disclose system optimization of maximal conversion for further application. PMID:25612092

  16. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-03-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.

  17. Preparation of Pd-Co-based nanocatalysts and their superior applications in formic acid decomposition and methanol oxidation.

    PubMed

    Qin, Yu-ling; Liu, Ya-cheng; Liang, Fei; Wang, Li-min

    2015-01-01

    Formic acid (FA) and methanol, as convenient hydrogen-containing materials, are most widely used for fuel cells. However, using suitable and low-cost catalysts to further improve their energy performance still is a matter of great significance. Herein, PdCo and PdCo@Pd nanocatalysts (NCs) are successfully prepared by the facile method. Pd 3d binding energy decreases due to the presence of Co. Consequently, PdCo@Pd NCs exhibit high catalytic activity and selectivity toward FA dehydrogenation at room temperature. The gas-generation rate at 30 min is 65.4 L h(-1)  g(-1) . PdCo/C has the worst catalytic performance in this reaction, despite the fact that it has a high gas-generation rate in the initial 30 min. Furthermore, both PdCo and PdCo@Pd NCs have enhanced electrocatalytic performance toward methanol oxidation. Their maximum currents are 966 and 1205 mA mg(-1) , respectively, which is much higher than monometallic Pd/C. PMID:25504901

  18. Synergic Catalysis of PdCu Alloy Nanoparticles within a Macroreticular Basic Resin for Hydrogen Production from Formic Acid.

    PubMed

    Mori, Kohsuke; Tanaka, Hiromasa; Dojo, Masahiro; Yoshizawa, Kazunari; Yamashita, Hiromi

    2015-08-17

    Highly dispersed PdCu alloy nanoparticles have been successfully prepared within a macroreticular basic resin bearing N(CH3 )2 functional groups. This previously unappreciated combination of alloy is first proven to be responsible for the efficient production of high-purity H2 from formic acid (HCOOH) dehydrogenation for chemical hydrogen storage. By the addition of Cu, the electronically promoted Pd sites show significantly higher catalytic activity as well as a better tolerance towards CO poisoning as compared to their monometallic Pd counterparts. Experimental and DFT calculation studies revealed not only the synergic alloying effect but also cooperative action by the N(CH3 )2 groups within the resin play crucial roles in achieving exceptional catalytic performances. In addition to the advantages such as, facile preparation method, free of additives, recyclable without leaching of active component, and suppression of unfavorable CO formation less than 3 ppm, the present catalytic system is cost-effective because of the superior catalytic activity compared with that of well-established precious PdAg or PdAu catalysts. The present catalytic system is particularly desirable for an ideal hydrogen vector in terms of potential industrial application for fuel cells. PMID:26178687

  19. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    PubMed Central

    2013-01-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies. PMID:23452438

  20. Characterization of Au and Bimetallic PtAu Nanoparticles on PDDA-Graphene Sheets as Electrocatalysts for Formic Acid Oxidation

    NASA Astrophysics Data System (ADS)

    Yung, Tung-Yuan; Liu, Ting-Yu; Huang, Li-Ying; Wang, Kuan-Syun; Tzou, Huei-Ming; Chen, Po-Tuan; Chao, Chi-Yang; Liu, Ling-Kang

    2015-09-01

    Nanocomposite materials of the Au nanoparticles (Au/PDDA-G) and the bimetallic PtAu nanoparticles on poly-(diallyldimethylammonium chloride) (PDDA)-modified graphene sheets (PtAu/PDDA-G) were prepared with hydrothermal method at 90 °C for 24 h. The composite materials Au/PDDA-G and PtAu/PDDA-G were evaluated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) for exploring the structural characterization for the electrochemical catalysis. According to TEM results, the diameter of Au and bimetallic PtAu nanoparticles is about 20-50 and 5-10 nm, respectively. X-ray diffraction (XRD) results indicate that both of PtAu and Au nanoparticles exhibit the crystalline plane of (111), (200), (210), and (311). Furthermore, XRD data also show the 2°-3° difference between pristine graphene sheets and the PDDA-modified graphene sheets. For the catalytic activity tests of Au/PDDA-G and PtAu/PDDA-G, the mixture of 0.5 M aqueous H2SO4 and 0.5 M aqueous formic acid was used as model to evaluate the electrochemical characterizations. The catalytic activities of the novel bimetallic PtAu/graphene electrocatalyst would be anticipated to be superior to the previous electrocatalyst of the cubic Pt/graphene.

  1. Highly efficient and autocatalytic H2O dissociation for CO2 reduction into formic acid with zinc

    PubMed Central

    Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

    2014-01-01

    Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH− complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal. PMID:24675820

  2. Communication: Protonation process of formic acid from the ionization and fragmentation of dimers induced by synchrotron radiation in the valence region

    NASA Astrophysics Data System (ADS)

    Arruda, Manuela S.; Medina, Aline; Sousa, Josenilton N.; Mendes, Luiz A. V.; Marinho, Ricardo R. T.; Prudente, Frederico V.

    2016-04-01

    The ionization and fragmentation of monomers of organic molecules have been extensively studied in the gas phase using mass spectroscopy. In the spectra of these molecules it is possible to identify the presence of protonated cations, which have a mass-to-charge ratio one unit larger than the parent ion. In this work, we investigate this protonation process as a result of dimers photofragmentation. Experimental photoionization and photofragmentation results of doubly deuterated formic acid (DCOOD) in the gas phase by photons in the vacuum ultraviolet region are presented. The experiment was performed by using a time-of-flight mass spectrometer installed at the Brazilian Synchrotron Light Laboratory and spectra for different pressure values in the experimental chamber were obtained. The coupled cluster approach with single and double substitutions was employed to assist the experimental analysis. Results indicate that protonated formic acid ions are originated from dimer dissociation, and the threshold photoionization of (DCOOD)ṡD+ is also determined.

  3. Effects of Soluble Lignin on the Formic Acid-Catalyzed Formation of Furfural: A Case Study for the Upgrading of Hemicellulose.

    PubMed

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2016-03-01

    A comprehensive study is presented on the conversion of hemicellulose sugars in liquors obtained from the fractionation of Miscanthus, spruce bark, sawdust, and hemp by using formic acid. Experimental tests with varying temperature (130-170 °C), formic acid concentration (10-80 wt%), carbohydrate concentrations, and lignin separation were carried out, and experimental data were compared with predictions obtained by reaction kinetics developed in a previous study. The conversions of xylose and arabinose into furfural were inherently affected by the presence of polymeric soluble lignin, decreasing the maximum furfural yields observed experimentally by up to 24%. These results were also confirmed in synthetic mixtures of pentoses with Miscanthus and commercial alkali lignin. This observation was attributed to side reactions involving intermediate stable sugar species reacting with solubilized lignin during the conversion of xylose into furfural. PMID:26805656

  4. MERCURY-NITRITE-RHODIUM-RUTHENIUM INTERACTIONS IN NOBLE METAL CATALYZED HYDROGEN GENERATION FROM FORMIC ACID DURING NUCLEAR WASTE PROCESSING AT THE SAVANNAH RIVER SITE - 136C

    SciTech Connect

    Koopman, D.; Pickenheim, B.; Lambert, D.; Newell, J; Stone, M.

    2009-09-02

    Chemical pre-treatment of radioactive waste at the Savannah River Site is performed to prepare the waste for vitrification into a stable waste glass form. During pre-treatment, compounds in the waste become catalytically active. Mercury, rhodium, and palladium become active for nitrite destruction by formic acid, while rhodium and ruthenium become active for catalytic conversion of formic acid into hydrogen and carbon dioxide. Nitrite ion is present during the maximum activity of rhodium, but is consumed prior to the activation of ruthenium. Catalytic hydrogen generation during pre-treatment can exceed radiolytic hydrogen generation by several orders of magnitude. Palladium and mercury impact the maximum catalytic hydrogen generation rates of rhodium and ruthenium by altering the kinetics of nitrite ion decomposition. New data are presented that illustrate the interactions of these various species.

  5. Indoor winter fumigation of Apis mellifera (Hymenoptera: Apidae) colonies infested with Varroa destructor (Acari: Varroidae) with formic acid is a potential control alternative in northern climates.

    PubMed

    Underwood, Robyn M; Currie, Robert W

    2004-04-01

    Formic acid treatment for the control of the ectoparasitic varroa mite, Varroa destructor Anderson & Trueman, infesting honey bee, Apis mellifera L., colonies is usually carried out as an in-hive outdoor treatment. This study examined the use of formic acid on wintered colonies kept indoors at 5 degrees C from 24 November 1999 to 24 March 2000. Colonies were placed in small treatment rooms that were not treated (control) or fumigated at three different concentrations of formic acid: low (mean 11.9 +/- 1.2 ppm), medium (mean 25.8 +/- 1.4 ppm), or high (mean 41.2 +/- 3.3 ppm), for 48 h on 22-24 January 2000. Queen bee, worker bee, and varroa mite mortality were monitored throughout the winter, and tracheal mite, Acarapis woodi (Rennie), prevalence and mean abundance of nosema, Nosema apis Zander, spores were assessed. This study revealed that formic acid fumigation of indoor-wintered honey bees is feasible and effective. The highest concentration significantly reduced the mean abundance of varroa mites and nosema spores without increasing bee mortality. Tracheal mite prevalence did not change significantly at any concentration, although we did not measure mortality directly. The highest concentration treatment killed 33.3% of queens compared with 4.8% loss in the control. Repeated fumigation periods at high concentrations or extended fumigation at low concentrations may increase the efficacy of this treatment method and should be tested in future studies. An understanding of the cause of queen loss and methods to prevent it must be developed for this method to be generally accepted. PMID:15154434

  6. Use of Activated Carbon in Packaging to Attenuate Formaldehyde-Induced and Formic Acid-Induced Degradation and Reduce Gelatin Cross-Linking in Solid Dosage Forms.

    PubMed

    Colgan, Stephen T; Zelesky, Todd C; Chen, Raymond; Likar, Michael D; MacDonald, Bruce C; Hawkins, Joel M; Carroll, Sophia C; Johnson, Gail M; Space, J Sean; Jensen, James F; DeMatteo, Vincent A

    2016-07-01

    Formaldehyde and formic acid are reactive impurities found in commonly used excipients and can be responsible for limiting drug product shelf-life. Described here is the use of activated carbon in drug product packaging to attenuate formaldehyde-induced and formic acid-induced drug degradation in tablets and cross-linking in hard gelatin capsules. Several pharmaceutical products with known or potential vulnerabilities to formaldehyde-induced or formic acid-induced degradation or gelatin cross-linking were subjected to accelerated stability challenges in the presence and absence of activated carbon. The effects of time and storage conditions were determined. For all of the products studied, activated carbon attenuated drug degradation or gelatin cross-linking. This novel use of activated carbon in pharmaceutical packaging may be useful for enhancing the chemical stability of drug products or the dissolution stability of gelatin-containing dosage forms and may allow for the 1) extension of a drug product's shelf-life when the limiting attribute is a degradation product induced by a reactive impurity, 2) marketing of a drug product in hotter and more humid climatic zones than currently supported without the use of activated carbon, and 3) enhanced dissolution stability of products that are vulnerable to gelatin cross-linking. PMID:27262203

  7. On the primary emission of formic acid from light duty gasoline vehicles and ocean-going vessels

    NASA Astrophysics Data System (ADS)

    Crisp, Timia A.; Brady, James M.; Cappa, Christopher D.; Collier, Sonya; Forestieri, Sara D.; Kleeman, Michael J.; Kuwayama, Toshihiro; Lerner, Brian M.; Williams, Eric J.; Zhang, Qi; Bertram, Timothy H.

    2014-12-01

    We present determinations of fuel-based emission factors for formic acid (EFHCOOH) from light duty gasoline vehicles (LDGVs) and in-use ocean-going vessels. Emission ratios, from which the emission factors were derived, were determined from LDGVs through measurement of HCOOH and carbon dioxide (CO2) in the exhaust of a fleet of eight LDGVs driven under the California Unified Cycle at the California Air Resources Board's Haagen-Smit Laboratory. Emission ratios from in-use ocean-going vessels were determined through direct measurement of HCOOH and CO2 in ship plumes intercepted by the R/V Atlantis during the 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign within 24 nautical miles of the California coast. The eight car fleet average EFHCOOH was 0.94 ± 0.32 (1σ) and 0.57 ± 0.18 mg (kg fuel)-1 for the cold start and hot running phases of the drive cycle, respectively. This difference suggests that catalytic converter performance and the air/fuel equivalence ratio are important metrics contributing to EFHCOOH. EFHCOOH was determined to be 1.94 ± 1.06 mg (kg fuel)-1 for a single diesel vehicle driven under highway driving conditions, higher on average than any individual LDGV tested. In comparison, HCOOH primary emissions from in-use ocean-going vessels were substantially larger, averaging 20.89 ± 8.50 mg (kg fuel)-1. On a global scale, HCOOH primary emissions from fossil fuel combustion are likely to be insignificant relative to secondary production mechanisms, however primary emissions may contribute more significantly on a finer, regional scale in urban locations.

  8. A Facile Synthesis of MPd (M=Co, Cu) Nanoparticles and Their Catalysis for Formic Acid Oxidation

    SciTech Connect

    Mazumder, Vismadeb; Chi, Miaofang; Mankin, Max; Liu, Yi; Metin, Onder; Sun, Daohua; More, Karren Leslie; Sun, Shouheng

    2012-01-01

    Monodisperse CoPd nanoparticles (NPs) were synthesized and studied for catalytic formic acid (HCOOH) oxidation (FAO). The NPs were prepared by coreduction of Co(acac)2 (acac = acetylacetonate) and PdBr2 at 260 C in oleylamine and trioctylphosphine, and their sizes (5-12 nm) and compositions (Co10Pd90 to Co60Pd40) were controlled by heating ramp rate, metal salt concentration, or metal molar ratios. The 8 nm CoPd NPs were activated for HCOOH oxidation by a simple ethanol wash. In 0.1 M HClO4 and 2 M HCOOH solution, their catalytic activities followed the trend of Co50Pd50 > Co60Pd40 > Co10Pd90 > Pd. The Co50Pd50 NPs had an oxidation peak at 0.4 V with a peak current density of 774 A/gPd. As a comparison, commercial Pd catalysts showed an oxidation peak at 0.75 V with peak current density of only 254 A/gPd. The synthesis procedure could also be extended to prepare CuPd NPs when Co(acac)2 was replaced by Cu(ac)2 (ac = acetate) in an otherwise identical condition. The CuPd NPs were less active catalysts than CoPd or even Pd for FAO in HClO4 solution. The synthesis provides a general approach to Pd-based bimetallic NPs and will enable further investigation of Pd-based alloy NPs for electro-oxidation and other catalytic reactions.

  9. Postmortem computed tomography and magnetic resonance imaging facilitates forensic autopsy in a fatal case of poisoning with formic acid, diphenhydramine, and ethanol.

    PubMed

    Berger, Florian; Steuer, Andrea E; Rentsch, Katharina; Gascho, Dominic; Stamou, Stamatios; Schärli, Sarah; Thali, Michael J; Krämer, Thomas; Flach, Patricia M

    2016-09-01

    A case of fatal poisoning by ingesting formic acid, diphenhydramine, and ethanol by a 25-year-old woman who committed suicide is presented. Prior to autopsy, postmortem computed tomography and postmortem magnetic resonance tomography were performed and revealed severe damage to the stomach, the left thoracic wall, and parts of the liver. Imaging detected acid-induced fluid-fluid level within the thoracic cavity (fat-equivalent fluid and necrotic pleural effusion). This case report illustrates that postmortem cross-sectional imaging may facilitate dissection of severely damaged or complex regions, and may provide additional information compared to autopsy and toxicological examinations alone. PMID:27427196

  10. Efficacy of adding folic acid to foods.

    PubMed

    Fajardo, Violeta; Varela-Moreiras, Gregorio

    2012-06-01

    In the past, food fortification along with nutritional education and the decrease in food costs relative to income have proven successful in eliminating common nutritional deficiencies. These deficiencies such as goiter, rickets, beriberi, and pellagra have been replaced with an entirely new set of "emergent deficiencies" that were not previously considered a problem [e.g., folate and neural tube defects (NTDs)]. In addition, the different nutrition surveys in so-called affluent countries have identified "shortfalls" of nutrients specific to various age groups and/or physiological status. Complex, multiple-etiology diseases, such as atherosclerosis, diabetes, cancer, and obesity have emerged. Food fortification has proven an effective tool for tackling nutritional deficiencies in populations; but today a more reasonable approach is to use food fortification as a means to support but not replace dietary improvement strategies (i. e. nutritional education campaigns). Folic acid (FA) is a potential relevant factor in the prevention of a number of pathologies. The evidence linking FA to NTD prevention led to the introduction of public health strategies to increase folate intakes: pharmacological supplementation, mandatory or voluntary fortification of staple foods with FA, and the advice to increase the intake of folate-rich foods. It is quite contradictory to observe that, regardless of these findings, there is only limited information on food folate and FA content. Data in Food Composition Tables and Databases are scarce or incomplete. Fortification of staple foods with FA has added difficulty to this task. Globally, the decision to fortify products is left up to individual food manufacturers. Voluntary fortification is a common practice in many countries. Therefore, the "worldwide map of vitamin fortification" may be analyzed. It is important to examine if fortification today really answers to vitamin requirements at different ages and/or physiological states. The

  11. Effect of concentration and exposure time on treatment efficacy against Varroa mites (Acari: Varroidae) during indoor winter fumigation of honey bees (Hymenoptera: Apidae) with formic acid.

    PubMed

    Underwood, Robyn M; Currie, Robert W

    2005-12-01

    The combination of the concentration of formic acid and the duration of fumigation (CT product) during indoor treatments of honey bee, Apis mellifera L., colonies to control the varroa mite, Varroa destructor Anderson & Trueman, determines the efficacy of the treatment. Because high concentrations can cause queen mortality, we hypothesized that a high CT product given as a low concentration over a long exposure time rather than as a high concentration over a short exposure time would allow effective control of varroa mites without the detrimental effects on queens. The objective of this study was to assess different combinations of formic acid concentration and exposure time with similar CT products in controlling varroa mites while minimizing the effect on worker and queen honey bees. Treated colonies were exposed to a low, medium, or high concentration of formic acid until a mean CT product of 471 ppm*d in room air was realized. The treatments consisted of a long-term low concentration of 19 ppm for 27 d, a medium-term medium concentration of 42 ppm for 10 d, a short-term high concentration of 53 ppm for 9 d, and an untreated control. Both short-term high-concentration and medium-term medium-concentration fumigation with formic acid killed varroa mites, with averages of 93 and 83% mortality, respectively, but both treatments also were associated with an increase in mortality of worker bees, queen bees, or both. Long-term low-concentration fumigation had lower efficacy (60% varroa mite mortality), but it did not increase worker or queen bee mortality. This trend differed slightly in colonies from two different beekeepers. Varroa mite mean abundance was significantly decreased in all three acid treatments relative to the control. Daily worker mortality was significantly increased by the short-term high concentration treatment, which was reflected by a decrease in the size of the worker population, but not an increase in colony mortality. Queen mortality was

  12. Mechanistic aspects of the rhodium-catalyzed enantioselective transfer hydrogenation of [alpha],[beta]-unsaturated carboxylic acids using formic acid/triethylamine (5:2) as the hydrogen source

    SciTech Connect

    Leitner, W. Universitaet Regensburg ); Brown, J.M. ); Brunner, H. )

    1993-01-13

    The mechanism of the rhodium-catalyzed enantioselective transfer hydrogenation of methylenebutanedioic acid (itaconic acid) (1) and related [alpha],[beta]-unsaturated carboxylic acids using formic acid/triethylamine (5:2) as the hydrogen source is investigated. Kinetic studies using [sup 1]H NMR spectroscopy are presented. Formic acid decomposition is shown to be the rate-limiting step with 1 as the substrate, while hydrogen transfer turns out to be rate determining in the case of (E)-(phenylmethylene)butanedioic acid ((E)-phenylitaconic acid) (3). Furthermore, extensive use is made of deuterium labeling and the analysis of part-deuterated products by [sup 1]H and [sup 13]C[l brace][sup 1]H,[sup 2]H[r brace] NMR spectroscopy. Taken together, these results indicate that the mechanism of rhodium-catalyzed transfer hydrogenation with formic acid/triethylamine as the hydrogen source most likely involves decarboxylation of a transient formate species to form hydridic complexes of rhodium, in which the Rh-H entity has a long lifetime relative to hydrogen transfer to the substrate. 40 refs., 5 figs., 1 tab.

  13. Tropospheric Emission Spectrometer (TES) satellite validations of ammonia, methanol, formic acid, and carbon monoxide over the Canadian oil sands

    NASA Astrophysics Data System (ADS)

    Shephard, M. W.; McLinden, C. A.; Cady-Pereira, K. E.; Luo, M.; Moussa, S. G.; Leithead, A.; Liggio, J.; Staebler, R. M.; Akingunola, A.; Makar, P.; Lehr, P.; Zhang, J.; Henze, D. K.; Millet, D. B.; Bash, J. O.; Zhu, L.; Wells, K. C.; Capps, S. L.; Chaliyakunnel, S.; Gordon, M.; Hayden, K.; Brook, J. R.; Wolde, M.; Li, S.-M.

    2015-09-01

    The wealth of air quality information provided by satellite infrared observations of ammonia (NH3), carbon monoxide (CO), formic acid (HCOOH), and methanol (CH3OH) is currently being explored and used for number of applications, especially at regional or global scales. These applications include air quality monitoring, trend analysis, emissions, and model evaluation. This study provides one of the first direct validations of Tropospheric Emission Spectrometer (TES) satellite retrieved profiles of NH3, CH3OH, and HCOOH through comparisons with coincident aircraft profiles. The comparisons are performed over the Canadian oil sands region during the intensive field campaign (August-September~2013) in support of the Joint Canada-Alberta Implementation Plan for the Oil Sands Monitoring (JOSM). The satellite/aircraft comparisons over this region during this period produced errors of: (i) + 0.08 ± 0.25 ppbv for NH3, (ii) + 7.5 ± 23 ppbv for CO, (iii) + 0.19 ± 0.46 ppbv for HCOOH, and (iv) -1.1 ± 0.39 ppbv for CH3OH. These values mostly agree with previously estimated retrieval errors; however, the relatively large negative bias in CH3OH and the significantly greater positive bias for larger HCOOH and CO values observed during this study warrant further investigation. Satellite and aircraft ammonia observations during the field campaign are also used in an initial effort to perform preliminary evaluations of Environment Canada's Global Environmental Multi-scale - Modelling Air quality and CHemistry (GEM-MACH) air quality modelling system at high-resolution (2.5 km × 2.5 km). These initial results indicate model under-prediction of ~ 0.6 ppbv (~ 60 %) for NH3, during the field campaign period. The TES-model CO comparison differences are ~ +20 ppbv (~ +20 %), but given that under these conditions the TES/aircraft comparisons also show a small positive TES CO bias indicates that the overall model under-prediction of CO is closer to ~ 10 % at 681 hPa (~ 3 km) during this

  14. Natural DNA-modified graphene/Pd nanoparticles as highly active catalyst for formic acid electro-oxidation and for the Suzuki reaction.

    PubMed

    Qu, Konggang; Wu, Li; Ren, Jinsong; Qu, Xiaogang

    2012-09-26

    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 π-π 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

  15. Temperature evolution of structure and bonding of formic acid and formate on fully oxidized and highly reduced CeO2(111)

    SciTech Connect

    Gordon, Wesley O; Xu, Ye; Mullins, David R; Overbury, Steven {Steve} H

    2009-01-01

    Adsorption of formate on oxide surfaces plays a role in water-gas shift (WGS) and other reactions related to H2 production and CO2 utilization. CeO2 is of particular interest because its reducibility affects the redox of organic molecules. In this work, the adsorption and thermal evolution of formic acid and formate on highly ordered films of fully oxidized CeO2(111) and highly reduced CeOx(111) surfaces have been studied using reflection absorption infrared spectroscopy (RAIRS) under ultra-high vacuum conditions, and the experimental results are combined with density functional theory (DFT) calculations to probe the identity, symmetry, and bonding of the surface intermediates. Disordered ice, ordered a-polymorph and molecular formic acid bonded through the carbonyl are observed at low temperatures. By 250 K, desorption and deprotonation lead to formate coexisting with hydroxyl on CeO2(111), identified to be a bridging bidentate formate species that is coordinated to Ce cations in nearly C2v symmetry and interacting strongly with neighboring H. Changes in the spectra at higher temperatures are consistent with additional tilting of the formate, resulting in Cs(2) or lower symmetry. This change in bonding is caused primarily by interaction with oxygen vacancies introduced by water desorption at 300 K. On reduced CeOx, multiple low-symmetry formate states exist likewise due to interactions with oxygen vacancies. Isotopic studies demonstrate that the formyl hydrogen does not contribute to H incorporated in hydroxyl on the surface, and that both formate oxygen atoms may exchange with lattice oxygen at 400 K. The combined experimental and theoretical results thus provide important insights on the surface reaction pathways of formic acid on ceria.

  16. Measuring acetic and formic acid by proton transfer reaction-mass spectrometry: sensitivity, humidity dependence, and quantifying interferences

    NASA Astrophysics Data System (ADS)

    Baasandorj, M.; Millet, D. B.; Hu, L.; Mitroo, D.; Williams, B. J.

    2014-10-01

    We present a detailed investigation of the factors governing the quantification of formic acid (FA), acetic acid (AA) and their relevant mass analogues by proton transfer reaction-mass spectrometry (PTR-MS), assess the underlying fragmentation pathways and humidity dependencies, and present a new method for separating FA and AA from their main isobaric interferences. PTR-MS sensitivities towards glycolaldehyde, ethyl acetate and peroxyacetic acid at m/z 61 are comparable to that for AA; when present, these species will interfere with ambient AA measurements by PTR-MS. Likewise, when it is present, dimethyl ether can interfere with FA measurements. On the other hand, for E/N = 125 Townsend (Td), the PTR-MS sensitivity towards ethanol at m/z 47 is 5-20× lower than for FA; ethanol will then only be an important interference when present in much higher abundance than FA. Sensitivity towards 2-propanol is <1% of that for AA, so that propanols will not in general represent a significant interference for AA. Hydrated product ions of AA, glycoaldehyde, and propanols occur at m/z 79, which is also commonly used to measure benzene. However, the resulting interference for benzene is only significant when E/N is low (<∼100 Td). Addition of water vapor affects the PTR-MS response to a given compound by (i) changing the yield for fragmentation reactions, and (ii) increasing the importance of ligand switching reactions. In the case of AA, sensitivity to the molecular ion increases with humidity at low E/N, but decreases with humidity at high E/N due to water-driven fragmentation. Sensitivity towards FA decreases with humidity throughout the full range of E/N. For glycoaldehyde and the alcohols, the sensitivity increases with humidity due to ligand switching reactions (at low E/N) and reduced fragmentation in the presence of water (at high E/N). Their role as interferences will typically be greatest at high humidity. For compounds such as AA where the humidity effect depends

  17. Measuring acetic and formic acid by proton-transfer-reaction mass spectrometry: sensitivity, humidity dependence, and quantifying interferences

    NASA Astrophysics Data System (ADS)

    Baasandorj, M.; Millet, D. B.; Hu, L.; Mitroo, D.; Williams, B. J.

    2015-03-01

    We present a detailed investigation of the factors governing the quantification of formic acid (FA), acetic acid (AA), and their relevant mass analogues by proton-transfer-reaction mass spectrometry (PTR-MS), assess the underlying fragmentation pathways and humidity dependencies, and present a new method for separating FA and AA from their main isobaric interferences. PTR-MS sensitivities towards glycolaldehyde, ethyl acetate, and peroxyacetic acid at m/z 61 are comparable to that for AA; when present, these species will interfere with ambient AA measurements by PTR-MS. Likewise, when it is present, dimethyl ether can interfere with FA measurements. For a reduced electric field (E/N) of 125 Townsend (Td), the PTR-MS sensitivity towards ethanol at m/z 47 is 5-20 times lower than for FA; ethanol will then only be an important interference when present in much higher abundance than FA. Sensitivity towards 2-propanol is <1% of that for AA, so that propanols will not in general represent a significant interference for AA. Hydrated product ions of AA, glycolaldehyde, and propanols occur at m/z 79, which is also commonly used to measure benzene. However, the resulting interference for benzene is only significant when E/N is low (≲100 Td). Addition of water vapor affects the PTR-MS response to a given compound by (i) changing the yield for fragmentation reactions and (ii) increasing the importance of ligand switching reactions. In the case of AA, sensitivity to the molecular ion increases with humidity at low E/N but decreases with humidity at high E/N due to water-driven fragmentation. Sensitivity towards FA decreases with humidity throughout the full range of E/N. For glycolaldehyde and the alcohols, the sensitivity increases with humidity due to ligand switching reactions (at low E/N) and reduced fragmentation in the presence of water (at high E/N). Their role as interferences will typically be greatest at high humidity. For compounds such as AA where the

  18. The electroplated Pd-Co alloy film on 316 L stainless steel and the corrosion resistance in boiling acetic acid and formic acid mixture with stirring

    NASA Astrophysics Data System (ADS)

    Li, Sirui; Zuo, Yu; Tang, Yuming; Zhao, Xuhui

    2014-12-01

    Pd-Co alloy films were deposited on 316 L stainless steel by electroplating. Scanning electronic microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, weight loss test and polarization test were used to determine the properties of the Pd-Co alloy films. The Pd-Co films show fine grain size, low porosity and obviously high micro-hardness. The Co content in the film can be controlled in a large range from 21.9 at.% to 57.42 at.%. Pd is rich on the Pd-Co film surface, which is benefit to increase the corrosion resistance. In boiling 90% acetic acid plus 10% formic acid mixture with 0.005 M Br- under stirring, the Pd-Co plated stainless steel samples exhibit evidently better corrosion resistance in contrast to Pd plated samples. The good corrosion resistance of the Pd-Co alloy film is explained by the better compactness, the lower porosity, and the obviously higher micro-hardness of the alloy films, which increases the resistance to erosion and retards the development of micro-pores in the film.

  19. Theoretical studies for the formation of γ-valero-lactone from levulinic acid and formic acid by homogeneous catalysis

    NASA Astrophysics Data System (ADS)

    Assary, Rajeev S.; Curtiss, Larry A.

    2012-07-01

    The γ-valero-lactone (GVL), a potential 'green' candidate for the production of liquid alkanes for transportation fuels, can be obtained by the hydrogenation of levulinic acid, a primary decomposition product of hexoses. On the search for the application of a bifunctional catalyst, we have identified that the versatile Shvo catalyst can be used to transfer the hydrogen required for the reduction of levulinic acid to GVL through a 2-hydroxy-pentanoic acid (2HP) intermediate. Density functional studies (DFT) have been employed here to compute the energetics for the conversion of levulinic acid to GVL. Additionally, we have investigated the potential application of an iron-based congener to replace the conventional Shvo catalyst due to its natural abundance and cost effectiveness.

  20. Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage.

    PubMed

    Gu, Xiaojun; Lu, Zhang-Hui; Jiang, Hai-Long; Akita, Tomoki; Xu, Qiang

    2011-08-10

    Bimetallic Au-Pd nanoparticles (NPs) were successfully immobilized in the metal-organic frameworks (MOFs) MIL-101 and ethylenediamine (ED)-grafted MIL-101 (ED-MIL-101) using a simple liquid impregnation method. The resulting composites, Au-Pd/MIL-101 and Au-Pd/ED-MIL-101, represent the first highly active MOF-immobilized metal catalysts for the complete conversion of formic acid to high-quality hydrogen at a convenient temperature for chemical hydrogen storage. Au-Pd NPs with strong bimetallic synergistic effects have a much higher catalytic activity and a higher tolerance with respect to CO poisoning than monometallic Au and Pd counterparts. PMID:21761819

  1. An ab initio study of the geometries, anharmonic force fields and fundamental vibration frequencies of cis- and trans-formic acid

    NASA Astrophysics Data System (ADS)

    Bock, Charles W.; Trachtman, Mendel; George, Philip

    1980-03-01

    The geometry, harmonic and anharmonic force fields, and fundamental vibration frequencies of cis- and trans-formic acid are studied ab initio in the 4-31G and (9,5) basis sets. For the more stable trans-conformer (i.e., trans with respect to CH and OH) comparisons are made between the predicted and observed anharmonic frequencies, and between the calculated harmonic force constants and those Redington derived from an analysis of experimental data. In the case of the less stable cis-conformer, for which there is as yet little experimental data, the calculations serve to predict values for the fundamental vibrational frequencies.

  2. Germanium(II) hydride mediated reduction of carbon dioxide to formic acid and methanol with ammonia borane as the hydrogen source.

    PubMed

    Jana, Anukul; Tavčar, Gašper; Roesky, Herbert W; John, Michael

    2010-10-28

    LGeOC(O)H (3) (L = CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)), from the straightforward conversion of LGeH (2) with CO(2), reacts with LiH(2)NBH(3) giving 2 and LiOC(O)H (4), while the corresponding reaction of 3 with H(3)NBH(3) after aqueous workup releases 2 and CH(3)OH (5). This opens the possibility to use hydride 2 as a mediator in the reduction of carbon dioxide to formic acid and methanol. PMID:20830405

  3. Metabolic pathway engineering based on metabolomics confers acetic and formic acid tolerance to a recombinant xylose-fermenting strain of Saccharomyces cerevisiae

    PubMed Central

    2011-01-01

    Background The development of novel yeast strains with increased tolerance toward inhibitors in lignocellulosic hydrolysates is highly desirable for the production of bio-ethanol. Weak organic acids such as acetic and formic acids are necessarily released during the pretreatment (i.e. solubilization and hydrolysis) of lignocelluloses, which negatively affect microbial growth and ethanol production. However, since the mode of toxicity is complicated, genetic engineering strategies addressing yeast tolerance to weak organic acids have been rare. Thus, enhanced basic research is expected to identify target genes for improved weak acid tolerance. Results In this study, the effect of acetic acid on xylose fermentation was analyzed by examining metabolite profiles in a recombinant xylose-fermenting strain of Saccharomyces cerevisiae. Metabolome analysis revealed that metabolites involved in the non-oxidative pentose phosphate pathway (PPP) [e.g. sedoheptulose-7-phosphate, ribulose-5-phosphate, ribose-5-phosphate and erythrose-4-phosphate] were significantly accumulated by the addition of acetate, indicating the possibility that acetic acid slows down the flux of the pathway. Accordingly, a gene encoding a PPP-related enzyme, transaldolase or transketolase, was overexpressed in the xylose-fermenting yeast, which successfully conferred increased ethanol productivity in the presence of acetic and formic acid. Conclusions Our metabolomic approach revealed one of the molecular events underlying the response to acetic acid and focuses attention on the non-oxidative PPP as a target for metabolic engineering. An important challenge for metabolic engineering is identification of gene targets that have material importance. This study has demonstrated that metabolomics is a powerful tool to develop rational strategies to confer tolerance to stress through genetic engineering. PMID:21219616

  4. Anomalous HNO3/NO(x) ratio of remote tropospheric air: Conversion of nitric acid to formic acid and NO(x)?

    NASA Technical Reports Server (NTRS)

    Chatfield, Robert B.

    1994-01-01

    The N oxidation ratio, (HNO3)/(NO(x)), in the free troposphere is measured at approx. 1 to 9 (averaging approx. 5), consistently lower than the values of 15-100 which known theory suggests to be reached rapidly. This discrepancy casts doubt on current models' abilities to predict effects of NO sources on remote (NO), and so also (O3) and (OH). HNO3-to-NO(x) recycling processes involving HCHO in solution are appealing explanations for the ratio. Known chemical theory are illustrated using a Lagrangian box model of the mid-troposphere which simulates characteristic episodes form NO(x) input to HNO3 washout. Ratio and budget constraint equations for No(y) can usefully restrict conceivable explanations of missing chemistry of fast nitrogen cycling; most explanations could be called 'fast-cycles' or 're-NO(x)-ification.' These equations also show how current global models may suggest spuriously good N oxidation ratios and errors in OH. Aerosol or cloud droplets reactions with HCHO may produce (a) formic acid (which needs an appropriate source) and NO(x), or alternatively, (b) hydroxymethyl nitrate (or methyl dinitrate), which might supply a large, variable amount of 'missing NO(y) not currently measurable except by NO(y) instruments.

  5. Palladium Nanoparticles Supported on Nitrogen and Sulfur Dual-Doped Graphene as Highly Active Electrocatalysts for Formic Acid and Methanol Oxidation.

    PubMed

    Zhang, Xin; Zhu, Jixin; Tiwary, Chandra Sekhar; Ma, Zhongyuan; Huang, Huajie; Zhang, Jianfeng; Lu, Zhiyong; Huang, Wei; Wu, Yuping

    2016-05-01

    Optimized designing of highly active electrocatalysts has been regarded as a critical point to the development of portable fuel cell systems with high power density. Here we report a facile and cost-effective strategy to synthesis of ultrafine Pd nanoparticles (NPs) supported on N and S dual-doped graphene (NS-G) nanosheets as multifunctional electrocatalysts for both direct formic acid fuel cell and direct methanol fuel cell. The incorporation of N and S atoms into graphene frameworks is achieved by a thermal treatment process, followed by the controlled growth of Pd NPs via a solvothermal approach. Owning to the unique structural features as well as the strong synergistic effects, the resulting Pd/NS-G hybrid exhibits outstanding electrocatalytic performance toward both formic acid and methanol electro-oxidation, such as higher anodic peak current densities and more exceptional catalytic stability than those of Pd/Vulcan XC-72R and Pd/undoped graphene catalysts. These findings open up new possibility in the construction of advanced Pd-based catalysts, which is conducive to solving the current bottlenecks of fuel cell technologies. PMID:27082661

  6. Composition-dependent electrocatalytic activity of palladium-iridium binary alloy nanoparticles supported on the multiwalled carbon nanotubes for the electro-oxidation of formic acid.

    PubMed

    Bao, Jianming; Dou, Meiling; Liu, Haijing; Wang, Feng; Liu, Jingjun; Li, Zhilin; Ji, Jing

    2015-07-22

    Surface-functionalized multiwalled carbon nanotubes (MWCNTs) supported Pd100-xIrx binary alloy nanoparticles (Pd100-xIrx/MWCNT) with tunable Pd/Ir atomic ratios were synthesized by a thermolytic process at varied ratios of bis(acetylacetonate) palladium(II) and iridium(III) 2,4-pentanedionate precursors and then applied as the electrocatalyst for the formic acid electro-oxidation. The X-ray diffraction pattern (XRD) and transmission electron microscope (TEM) analysis showed that the Pd100-xIrx alloy nanoparticles with the average size of 6.2 nm were uniformly dispersed on the MWCNTs and exhibited a single solid solution phase with a face-centered cubic structure. The electrocatalytic properties were evaluated through the cyclic voltammetry and chronoamperometry tests, and the results indicated that both the activity and stability of Pd100-xIrx/MWCNT were strongly dependent on the Pd/Ir atomic ratios: the best electrocatalytic performance in terms of onset potential, current density, and stability against CO poisoning was obtained for the Pd79Ir21/MWCNT. Moreover, compared with pure Pd nanoparticles supported on MWCNTs (Pd/MWCNT), the Pd79Ir21/MWCNT exhibited enhanced steady-state current density and higher stability, as well as maintained excellent electrocatalytic activity in high concentrated formic acid solution, which was attributed to the bifunctional effect through alloying Pd with transition metal. PMID:26132867

  7. Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Wook; Jin, Min-Ho; Park, Ji Chan; Lee, Chun-Boo; Oh, Duckkyu; Lee, Sung-Wook; Park, Jin-Woo; Park, Jong-Soo

    2015-10-01

    The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h-1) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol.

  8. Catalytic performance comparison of shape-dependent nanocrystals and oriented ultra thin films of Pt4Cu alloy in the formic acid oxidation process

    NASA Astrophysics Data System (ADS)

    Bromberg, Lori Ana

    Research efforts continue to focus on the development of viable and cost effective fuel cell catalysts with minimized Pt content. This work presents a comparison study between Pt4Cu nanocubes and nano-octahedra as well as Pt4Cu (100) and (111) thin films used as catalysts for formic acid oxidation. The paper introduces a novel synthetic method for Pt 4Cu nano-octahedra and it also demonstrates for the first time the use of surface limited redox replacement of Pb underpotentially deposited layer for epitaxial growth of thin alloy films. Overall, the nanoparticle catalysts exhibit superior performance in terms of durability when compared to their thin film counterparts, but feature nearly five-fold lower activity. As a result it was determined that both types of catalysts accumulate nearly equal charge density in their lifespan. In terms of crystallographic orientation, the results indicate that the nanocubes and Pt4Cu (100) thin films outperform the nano-octahedra and Pt4Cu (111) thin films in terms of durability but feature equal to slightly lower activity. This significant difference in durability of catalysts with different crystallographic orientation is attributed to interplay of passivation (from CO poisoning and Pt oxidation) and dissolution of Pt. When compared to pure Pt catalysts (nanoparticles and thin films), all of the Pt4Cu catalysts in this work exhibit superior performance towards formic acid oxidation in terms of activity and durability.

  9. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    SciTech Connect

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; Liu, Haiqing; Wong, Stanislaus S.

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication of crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.

  10. Computational study of the adsorption of methanol, formic acid, and formaldehyde on the β-SiC(100)-3x2 surface

    NASA Astrophysics Data System (ADS)

    Adhikari, Lekh; Casey, Sean

    2009-11-01

    The absorption of methanol, formic acid, and formaldehyde on the Si-rich β-SiC(100)-(3x2) surface has been studied using density functional theory (DFT) computational methods and small clusters to model the surface reactivity. A single cluster dimer model is used to calculate energies after the interaction of adsorbates on the surface. The dissociative adsorption of methanol on the SiC(100)-3x2 surface is predicted to take place facilely, giving rise to Si-OCH3 and Si-H surface species and followed a path similar to that predicted for Si(100)-2x1 surface. The reaction is highly exothermic and predicted to occur with essentially no barrier. Formaldehyde is also predicted to adsorb with essentially no barrier on the SiC(100)-3x2 surface with formation of a 4-member ring on the surface. This adsorption is also exothermic and similar to the corresponding Si(100)-2x1 surface. This result shows that the carbonyl group can undergo cycloaddition onto the SiC(100) surface. Formic acid is also predicted to undergo dissociative chemisorption on the SiC(100) surface with the formation of Si-OCOH and Si-H surface species. This process is also highly exothermic (-283.1 kJ/mol) and essentially barrierless.

  11. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    DOE PAGESBeta

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; Liu, Haiqing; Wong, Stanislaus S.

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication ofmore » crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.« less

  12. No catalyst addition and highly efficient dissociation of H2O for the reduction of CO2 to formic acid with Mn.

    PubMed

    Lyu, Lingyun; Zeng, Xu; Yun, Jun; Wei, Feng; Jin, Fangming

    2014-05-20

    The "greenhouse effect" caused by the increasing atmospheric CO2 level is becoming extremely serious, and thus, the reduction of CO2 emissions has become an extensive, urgent, and long-term task. The dissociation of water for CO2 reduction with solar energy is regarded as one of the most promising methods for the sustainable development of the environment and energy. However, a high solar-to-fuel efficiency keeps a great challenge. In this work, the first observation of a highly effective, highly selective, and robust system of dissociating water for the reduction of carbon dioxide (CO2) into formic acid with metallic manganese (Mn) is reported. A considerably high formic acid yield of more than 75% on a carbon basis from NaHCO3 was achieved with 98% selectivity in the presence of simple commercially available Mn powder without the addition of any catalyst, and the proposed process is exothermic. Thus, this study may provide a promising method for the highly efficient dissociation of water for CO2 reduction by combining solar-driven thermochemistry with the reduction of MnO into Mn. PMID:24787746

  13. Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid.

    PubMed

    Lee, Dong-Wook; Jin, Min-Ho; Park, Ji Chan; Lee, Chun-Boo; Oh, Duckkyu; Lee, Sung-Wook; Park, Jin-Woo; Park, Jong-Soo

    2015-01-01

    The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h(-1)) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol. PMID:26515193

  14. Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid

    PubMed Central

    Lee, Dong-Wook; Jin, Min-Ho; Park, Ji Chan; Lee, Chun-Boo; Oh, Duckkyu; Lee, Sung-Wook; Park, Jin-Woo; Park, Jong-Soo

    2015-01-01

    The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h−1) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol. PMID:26515193

  15. Formic Acid-Based Direct, On-Plate Testing of Yeast and Corynebacterium Species by Bruker Biotyper Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

    PubMed Central

    Theel, Elitza S.; Schmitt, Bryan H.; Hall, Leslie; Cunningham, Scott A.; Walchak, Robert C.; Patel, Robin

    2012-01-01

    An on-plate testing method using formic acid was evaluated on the Bruker Biotyper matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry system using 90 yeast and 78 Corynebacterium species isolates, and 95.6 and 81.1% of yeast and 96.1 and 92.3% of Corynebacterium isolates were correctly identified to the genus and species levels, respectively. The on-plate method using formic acid yielded identification percentages similar to those for the conventional but more laborious tube-based extraction. PMID:22760034

  16. Nanocrystalline hard chromium electrodeposition from trivalent chromium bath containing carbamide and formic acid: Structure, composition, electrochemical corrosion behavior, hardness and wear characteristics of deposits

    NASA Astrophysics Data System (ADS)

    Danilov, F. I.; Protsenko, V. S.; Gordiienko, V. O.; Kwon, S. C.; Lee, J. Y.; Kim, M.

    2011-07-01

    The paper is devoted to the structure, composition and properties investigations of coatings obtained from a sulfate trivalent chromium bath containing formic acid and carbamide as the complexing agents. The results indicate that the deposits have a nanocrystalline type of structure-there are regions with atomic ordered arrangement in bulk material with the average size of 3-5 nm. Carbon is present as chromium carbide within the coating and it is distributed uniformly inside of the deposit. The deposits under study exhibit particular electrochemical behavior (absence of the active dissolution range in acid solution). The hardness of these coatings does not differ noticeably from that typical of coatings obtained in Cr(VI)-based baths. The wear characteristics of the deposits from the proposed bath are somewhat better than in the case of a common hexavalent chromium bath.

  17. Infrared spectroscopy study of adsorption and photodecomposition of formic acid on reduced and defective rutile TiO{sub 2} (110) surfaces

    SciTech Connect

    Mattsson, Andreas Österlund, Lars; Hu, Shuanglin; Hermansson, Kersti

    2014-11-01

    Adsorption and photodecomposition of formic acid on rutile TiO{sub 2} (110) have been investigated with infrared reflection–absorption spectroscopy (IRRAS) employing p- and s-polarized light along the [001] and [11{sup ¯}0] crystal directions. The single crystal surfaces were prepared either by sputtering and annealing in ultrahigh vacuum (UHV) to obtain a reduced surface (r-TiO{sub 2}), or by sputtering without annealing to create a rough, highly defective surface (sp-TiO{sub 2}). Results are compared with corresponding measurements on rutile nanocrystals performed in synthetic air. IRRAS spectra obtained on r-TiO{sub 2} and rutile nanocrystals are very similar, and show that in both cases formic acid dissociates and is predominately adsorbed as a bridging bidentate formate species, and that the formate adsorption structure on the nanocrystals is dominated by interactions with majority (110) surfaces. In contrast, the IRRAS spectra on sp-TiO{sub 2} are different, with only minor spectral features associated with (110) surfaces and lost azimuthal symmetry, both of which imply changed adsorption geometry due to bonding to low-coordinated Ti atoms with lower valences. The UV-induced rate of formate photodecomposition is about 30 times higher on rutile nanocrystals in synthetic air compared with sp-TiO{sub 2} under UHV conditions, and even larger than on r-TiO{sub 2}. These differences are explained by the lack of oxygen and limited hydroxyl coverage under UHV conditions. The difference in reactivity between the r-TiO{sub 2} and sp-TiO{sub 2} surfaces is attributed to a high concentration of strongly bonded bridging bidentate formate species on the (110) surface, which lowers its reactivity. The results point to a pressure gap where the availability of molecular oxygen and the hydroxyl concentration limit the photoreactivity in UHV leading to an almost 20-fold decrease of the formate degradation rate in UHV. In contrast, the structure represented by the single

  18. Synthesis of ferromagnetic nanoparticles, formic acid oxidation catalyst nanocomposites, and late-transition metal-boride intermetallics by unique synthetic methods and single-source precursors

    NASA Astrophysics Data System (ADS)

    Wellons, Matthew S.

    The design, synthesis, and characterization of magnetic alloy nanoparticles, supported formic acid oxidation catalysts, and superhard intermetallic composites are presented. Ferromagnetic equatomic alloy nanoparticles of FePt, FePd, and CoPt were synthesized utilizing single-source heteronuclear organometallic precursors supported on an inert water-soluble matrix. Direct conversion of the precursor-support composite to supported ferromagnetic nanoparticles occurs under elevated temperatures and reducing conditions with metal-ion reduction and minimal nanoparticle coalescence. Nanoparticles were easily extracted from the support by addition of water and characterized in structure and magnetic properties. Palladium and platinum based nanoparticles were synthesized with microwave-based and chemical metal-ion reduction strategies, respectively, and tested for catalytic performance in a direct formic acid fuel cell (DFAFC). A study of palladium carbide nanocomposites with various carbonaceous supports was conducted and demonstrated strong activity comparable to commercially available palladium black, but poor catalytic longevity. Platinum-lead alloy nanocomposites synthesized with chemical reduction and supported on Vulcan carbon demonstrated strong activity, excellent catalytic longevity, and were subsequently incorporated into a prototype DFAFC. A new method for the synthesis of superhard ceramics on polymer substrates called Confined Plasma Chemical Deposition (CPCD) was developed. The CPCD method utilizes a tuned Free Electron Laser to selectively decompose the single-source precursor, Re(CO)4(B3H8), in a plasma-like state resulting in the superhard intermetallic ReB2 deposited on polymer substrates. Extension of this method to the synthesis of other hard of superhard ceramics; WB4, RuB2, and B4C was demonstrated. These three areas of research show new synthetic methods and novel materials of technological importance, resulting in a substantial advance in their

  19. Scanning tunneling microscopy study of formate species synthesized from CO{sub 2} hydrogenation and prepared by adsorption of formic acid over Cu(111)

    SciTech Connect

    Fujitani, T.; Choi, Y.; Sano, M.; Kushida, Y.; Nakamura, J.

    2000-02-17

    The adsorption structure of formate species on Cu(111), prepared by two different methods, was studied using ultrahigh vacuum scanning tunneling microscopy (UHV-STM), that is, the synthesis by the hydrogenation of CO{sub 2} at atmospheric pressure and the adsorption of formic acid on an oxygen-precovered Cu(111). Linear chains of formate molecules were imaged by the hydrogenation of CO{sub 2} by STM at low formate coverage with the distance to the nearest neighbor of the formate species estimated to be 5.0 {+-} 0.2{angstrom}, twice that of the nearest Cu--Cu neighbor. The adsorption phase of formate thus grows linearly at the initial stage by an anisotropic attractive interaction between the formate species. The ordered structure of the formate species changed in the order of p(2 x 4), c(2 x 8), (7 x 7), p(2 x 3), (5 x 5), and c(2 x 4) with increasing formate coverage, indicating that various ordered structures appeared corresponding to the small change in the formate coverage. All the formate structures, except for (7 x 7) and (5 x 5), consisted of the same chain as observed at low coverage, with the distance between the formate chains, resulting in a lowering of the adsorption energy of the formate species as reported in the literature. On the other hand, (4 x 4) and (3 x 7/2) structures were observed upon exposing the Cu(111) surface to formic acid at 2 and 15 L, respectively, showing no chain structure of the formate species. At low formate coverage, no molecular image was observed, indicating that the formate species diffuses more rapidly than the scanning of the STM tip. Thus, the adsorption structure of formate on Cu(111) was found to be different depending on the preparation method. It is suggested that the difference in the adsorption structure strongly influences the rate constant of the previously reported formate decomposition.

  20. Matrix Isolation Infrared Spectroscopy of an O-H···π Hydrogen-Bonded Complex between Formic Acid and Benzene.

    PubMed

    Banerjee, Pujarini; Bhattacharya, Indrani; Chakraborty, Tapas

    2016-05-26

    Mid-infrared spectra of an O-H···π hydrogen-bonded 1:1 complex between formic acid and benzene were measured by isolating the complex in an argon matrix at a temperature of 8 K. The O-H stretching fundamental of formic acid (νO-H) undergoes a red shift of 120 cm(-1), which is the largest among the known π-hydrogen bonded complexes of an O-H donor with respect to benzene as acceptor. Electronic structure theory methods were used extensively to suggest a suitable geometry of the complex that is consistent with a recent study performed at CCSD(T)/CBS level by Zhao et al. (J. Chem. Theory Comput. 2009, 5, 2726-2733), as well as with the measured IR spectral shifts of the present study. It has been determined that density functional theory (DFT) D functionals as well as parametrized DFT functionals like M06-2X, in conjunction with modestly sized basis sets like 6-31G (d, p), are sufficient for correct predictions of the spectral shifts observed in our measurement and also for reproducing the value of the binding energy reported by Zhao et al. We also verified that these low-cost methods are sufficient in predicting the νO-H spectral shifts of an analogous O-H···π hydrogen-bonded complex between phenol and benzene. However, some inconsistencies with respect to shifts of νO-H arise when diffuse functions are included in the basis sets, and the origin of this anomaly is shown to lie in the predicted geometry of the complex. Natural bond orbital (NBO) and atoms-in-molecule (AIM) analyses were performed to correlate the spectral behavior of the complex with its geometric parameters. PMID:27163753

  1. Improved 1,3-propanediol production by engineering the 2,3-butanediol and formic acid pathways in integrative recombinant Klebsiella pneumoniae.

    PubMed

    Wu, Zhe; Wang, Zhe; Wang, Guoqing; Tan, Tianwei

    2013-10-20

    In the biotechnological process, insufficient cofactor NADH and multiple by-products restrain the final titer of 1,3-propanediol (1,3-PD). In this study, 1,3-PD production was improved by engineering the 2,3-butanediol (2,3-BD) and formic acid pathways in integrative recombinant Klebsiella pneumoniae. The formation of 2,3-BD is catalysed by acetoin reductase (AR). An inactivation mutation of the AR in K. pneumoniae CF was generated by insertion of a formate dehydrogenase gene. Inactivation of AR and expression of formate dehydrogenase reduced 2,3-BD formation and improved 1,3-PD production. Fermentation results revealed that intracellular metabolic flux was redistributed pronouncedly. The yield of 1,3-PD reached 0.74 mol/mol glycerol in flask fermentation, which is higher than the theoretical yield. In 5 L fed-batch fermentation, the final titer and 1,3-PD yield of the K. pneumoniae CF strain reached 72.2 g/L and 0.569 mol/mol, respectively, which were 15.9% and 21.7% higher than those of the wild-type strain. The titers of 2,3-BD and formic acid decreased by 52.2% and 73.4%, respectively. By decreasing the concentration of all nonvolatile by-products and by increasing the availability of NADH, this study demonstrates an important strategy in the metabolic engineering of 1,3-PD production by integrative recombinant hosts. PMID:23665191

  2. Structural characterization of electron-induced proton transfer in the formic acid dimer anion, (HCOOH)2-, with vibrational and photoelectron spectroscopies.

    PubMed

    Gerardi, Helen K; DeBlase, Andrew F; Leavitt, Christopher M; Su, Xiaoge; Jordan, Kenneth D; McCoy, Anne B; Johnson, Mark A

    2012-04-01

    The (HCOOH)(2) anion, formed by electron attachment to the formic acid dimer (FA(2)), is an archetypal system for exploring the mechanics of the electron-induced proton transfer motif that is purported to occur when neutral nucleic acid base-pairs accommodate an excess electron [K. Aflatooni, G. A. Gallup, and P. D. Burrow, J. Phys. Chem. A 102, 6205 (1998); J. H. Hendricks, S. A. Lyapustina, H. L. de Clercq, J. T. Snodgrass, and K. H. Bowen, J. Chem Phys. 104, 7788 (1996); C. Desfrancois, H. Abdoul-Carime, and J. P. Schermann, ibid. 104, 7792 (1996)]. The FA(2) anion and several of its H∕D isotopologues were isolated in the gas phase and characterized using Ar-tagged vibrational predissociation and electron autodetachment spectroscopies. The photoelectron spectrum of the FA(2) anion was also recorded using velocity-map imaging. The resulting spectroscopic information verifies the equilibrium FA(2)(-) geometry predicted by theory which features a symmetrical, double H-bonded bridge effectively linking together constituents that most closely resemble the formate ion and a dihydroxymethyl radical. The spectroscopic signatures of this ion were analyzed with the aid of calculated anharmonic vibrational band patterns. PMID:22482563

  3. Comparison of the levels of 8-hydroxyguanine in DNA as measured by gas chromatography mass spectrometry following hydrolysis of DNA by Escherichia coli Fpg protein or formic acid

    PubMed Central

    Rodriguez, Henry; Jurado, Juan; Laval, Jacques; Dizdaroglu, Miral

    2000-01-01

    8-hydroxyguanine (8-OH-Gua) is one of many lesions generated in DNA by oxidative processes including free radicals. It is the most extensively investigated lesion, due to its miscoding properties and its potential role in mutagenesis, carcinogenesis and aging, and also to the existence of analytical methods using HPLC and gas chromatography mass spectrometry (GC/MS). Some studies raised the possibility of artifacts generated during sample preparation. We investigated several experimental conditions in order to eliminate possible artifacts during the measurement of 8-OH-Gua by GC/MS. Derivatization has been reported to produce artifacts by oxidation of guanine to 8-OH-Gua in acid-hydrolysates of DNA, although the extent of artifacts seems to depend on experimental conditions. For removal of 8-OH-Gua from DNA, we used either formic acid hydrolysis or specific enzymatic hydrolysis with Escherichia coli Fpg protein. Derivatization of enzyme-hydrolysates should not generate additional 8-OH-Gua because of the absence of guanine, which is not released by the enzyme, whereas guanine released by acid may be oxidized to yield 8-OH-Gua. The measurement of 8-OH-Gua in calf thymus DNA by GC/isotope-dilution MS (GC/IDMS) using these two different hydrolyses yielded similar levels of 8-OH-Gua. This indicated that no artifacts occurred during derivatization of acid-hydrolysates of DNA. Pyridine instead of acetonitrile and room temperature were used during derivatization. Pyridine reduced the level of 8-OH-Gua, when compared with acetonitrile, indicating its potential to prevent oxidation. Two different stable-isotope labeled analogs of 8-OH-Gua used as internal standards for GC/IDMS analysis yielded similar results. A comparison of the present results with the results of recent trials by the European Standards Committee for Oxidative DNA Damage (ESCODD) is also presented. PMID:10908368

  4. Quantum free energy landscapes from ab initio path integral metadynamics: Double proton transfer in the formic acid dimer is concerted but not correlated.

    PubMed

    Ivanov, Sergei D; Grant, Ian M; Marx, Dominik

    2015-09-28

    With the goal of computing quantum free energy landscapes of reactive (bio)chemical systems in multi-dimensional space, we combine the metadynamics technique for sampling potential energy surfaces with the ab initio path integral approach to treating nuclear quantum motion. This unified method is applied to the double proton transfer process in the formic acid dimer (FAD), in order to study the nuclear quantum effects at finite temperatures without imposing a one-dimensional reaction coordinate or reducing the dimensionality. Importantly, the ab initio path integral metadynamics technique allows one to treat the hydrogen bonds and concomitant proton transfers in FAD strictly independently and thus provides direct access to the much discussed issue of whether the double proton transfer proceeds via a stepwise or concerted mechanism. The quantum free energy landscape we compute for this H-bonded molecular complex reveals that the two protons move in a concerted fashion from initial to product state, yet world-line analysis of the quantum correlations demonstrates that the protons are as quantum-uncorrelated at the transition state as they are when close to the equilibrium structure. PMID:26429008

  5. Fuel blends: Enhanced electro-oxidation of formic acid in its blend with methanol at platinum nanoparticles modified glassy carbon electrodes

    NASA Astrophysics Data System (ADS)

    El-Deab, Mohamed S.; El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Anadouli, Bahgat E.

    2015-07-01

    The current study addresses, for the first time, the enhanced direct electro-oxidation of formic acid (FA) at platinum-nanoparticles modified glassy carbon (nano-Pt/GC) electrode in the presence of methanol (MeOH) as a blending fuel. This enhancement is probed by: (i) the increase of the direct oxidation current of FA to CO2 (Ipd, dehydrogenation pathway), (ii) suppressing the dehydration pathway (Ipind, producing the poisoning intermediate CO) and (iii) a favorable negative shift of the onset potential of Ibd with increasing the mole fraction of MeOH in the blend. Furthermore, the charge of the direct FA oxidation in 0.3 M FA + 0.3 M MeOH blend is by 14 and 21times higher than that observed for 0.3 M FA and 0.3 M MeOH, respectively. MeOH is believed to adsorb at the Pt surface sites and thus disfavor the "non-faradaic" dissociation of FA (which produces the poisoning CO intermediate), i.e., MeOH induces a high CO tolerance of the Pt catalyst. The enhanced oxidation activity indicates that FA/MeOH blend is a promising fuel system.

  6. Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

    SciTech Connect

    Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2015-12-21

    Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol at a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.

  7. A surfactant-free strategy for synthesizing reduced graphene oxide supported palladium nanoparticles with enhanced electrocatalytic performance towards formic acid oxidation

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    A simple noncovalent method is used to graft sulfonate (-SO3H) groups on a graphene oxide (GO) surface by the π-π stacking interaction between 1-propylsulfonic-3-methylimidazolium chloride and GO. The immobilization of sulfonate groups on the GO surface is confirmed by various physical techniques, such as X-ray photoelectron spectroscopy, ultraviolet and visible spectroscopy, and zeta potential analysis, etc. The as-prepared sulfonate functionalized GO composites (GO-SO3H) are further used as supporting material to anchor PdO·H2O nanoparticles through the slow hydrolysis of PdCl2. The sulfonate functionalized reduced GO composites (rGO-SO3H) supported Pd nanoparticles composites (Pd/rGO-SO3H) are obtained through the simultaneous reduction of PdO·H2O and the GO-SO3H with sodium borohydride. As shown by transmission electron microscopy, Pd nanoparticles with good dispersity effectively anchor on the rGO-SO3H surface. The as-prepared Pd/rGO-SO3H composites display the improved electrocatalytic activity and long-term stability towards the formic acid oxidation reaction compared to the un-sulfonated counterpart.

  8. Remarkable activity of PdIr nanoparticles supported on the surface of carbon nanotubes pretreated via a sonochemical process for formic acid electro-oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Jinwei; Li, Yuanjie; Liu, Shuangren; Wang, Gang; Tian, Jing; Jiang, Chunping; Zhu, Shifu; Wang, Ruilin

    2013-12-01

    It was reported for the first time that the surface treated multi-walled carbon nanotubes supported PdIr (PdIr/CNT-SCP) catalyst presents remarkable electrocatalytic activity and stability for formic acid electro-oxidation (FAEO). The surface of CNTs was functionalized by a sonochemical process for the deposition of PdIr nanoparticles (NPs). The XRD and TEM characterizations show that the prepared PdIr/CNT-SCP catalyst has small mean size and good dispersion of PdIr NPs on CNTs. The electrochemical measurements show that the onset and anodic peak potentials of FAEO on PdIr/CNT-SCP catalyst are 60 and 50 mV more negative than that on the commercial Pd/C catalyst. The mass-normalized peak current density of PdIr/CNT-SCP is 3365 mA mg-1Pd, which is 4.5, 1.4 and 2.7 times higher than that of PdIr/CNT-Untreated, PdIr/C-SCP and commercial Pd/C, respectively. It demonstrates the promotion of Ir and functionalized CNTs to Pd for FAEO.

  9. N-doped carbon dots derived from bovine serum albumin and formic acid with one- and two-photon fluorescence for live cell nuclear imaging.

    PubMed

    Tan, Mingqian; Li, Xintong; Wu, Hao; Wang, Beibei; Wu, Jing

    2015-12-01

    Carbon dots with both one- and two-photon fluorescence have drawn great attention for biomedical imaging. Herein, nitrogen-doped carbon dots were facilely developed by one-pot hydrothermal method using bovine serum albumin and formic acid as carbon sources. They are highly water-soluble with strong fluorescence when excited with ultraviolet or near infrared light. The carbon dots have a diameter of ~8.32 nm and can emit strong two-photon induced fluorescence upon excitation at 750 nm with a femtosecond laser. X-ray photoelectron spectrometer analysis revealed that the carbon dots contained three components, C, N and O, corresponding to the peak at 285, 398 and 532 eV, respectively. The Fourier-transform infrared spectroscopy analysis revealed that there are carboxyl and carboxylic groups on the surface, which allowed further linking of functional molecules. pH stability study demonstrated that the carbon dots are able to be used in a wide range of pH values. The fluorescence mechanism is also discussed in this study. Importantly, these carbon dots are biocompatible and highly photostable, which can be directly applied for both one- and two-photon living cell imaging. After proper surface functionalization with TAT peptide, they can be used as fluorescent probes for live cell nuclear-targeted imaging. PMID:26381697

  10. Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation

    PubMed Central

    Lee, Dong-Wook; Jin, Min-Ho; Lee, Young-Joo; Park, Ju-Hyoung; Lee, Chun-Boo; Park, Jong-Soo

    2016-01-01

    The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method. PMID:27198855

  11. Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Wook; Jin, Min-Ho; Lee, Young-Joo; Park, Ju-Hyoung; Lee, Chun-Boo; Park, Jong-Soo

    2016-05-01

    The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method.

  12. Highly robust hydrogen generation by bio-inspired Ir complexes for dehydrogenation of formic acid in water: Experimental and theoretical mechanistic investigations at different pH

    SciTech Connect

    Wang, Wan -Hui; Fujita, Etsuko; Ertem, Mehmed Z.; Xu, Shaoan; Onishi, Naoya; Manaka, Yuichi; Suna, Yuki; Kambayashi, Hide; Muckerman, James T.; Himeda, Yuichiro

    2015-07-30

    Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6) achieved a turnover frequency (TOF) of 322,000 h⁻¹ at 100 °C, which is higher than ever reported. The novel catalysts are very stable and applicable in highly concentrated FA. For instance, complex 3 (1 μmol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 °C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a “speciation” approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H₂ generation from FA.

  13. Highly robust hydrogen generation by bio-inspired Ir complexes for dehydrogenation of formic acid in water: Experimental and theoretical mechanistic investigations at different pH

    DOE PAGESBeta

    Wang, Wan -Hui; Fujita, Etsuko; Ertem, Mehmed Z.; Xu, Shaoan; Onishi, Naoya; Manaka, Yuichi; Suna, Yuki; Kambayashi, Hide; Muckerman, James T.; Himeda, Yuichiro

    2015-07-30

    Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6) achieved a turnover frequency (TOF) of 322,000 h⁻¹ at 100 °C, which is higher than ever reported. The novel catalysts are very stablemore » and applicable in highly concentrated FA. For instance, complex 3 (1 μmol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 °C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a “speciation” approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H₂ generation from FA.« less

  14. FTIR spectra of the ν6 and ν8 bands of 13C formic acid molecule—Assignment of FIR-laser lines

    NASA Astrophysics Data System (ADS)

    Baskakov, O.; Horneman, V.-M.; Alanko, S.; Lohilahti, J.

    2008-05-01

    Two interacting vibrational modes ν6 and ν8 of 13C species of formic acid have been studied with high resolution FTIR spectroscopy in the range 900-1300 cm -1 with an instrumental resolution of 0.0018 cm -1. More than 10 000 lines have been assigned and fitted with a RMS deviation of 0.00024 cm -1. The band centers, as well as the rotational, quartic and sextic centrifugal distortion parameters and 6 interaction parameters have been determined. The obtained parameters have enabled the assignments of 24 FIR laser emissions of this molecule observed previously by Dangoisse and Glorieux [D. Dangoisse, P. Glorieux, J. Mol. Spectrosc. 92 (1982) 283-297], Luis et al. [G.M.R.S. Luis, E.M. Telles, A. Scalabrin, D. Pereira, IEEE J. Quantum. Electron. QE-34 (1998) 767-769], and Bertolini et al. [A. Bertolini, G. Carelli, C.A. Massa, A. Moretti, F. Strumia, Infrared Phys. Technol. 40 (1999) 33-36].

  15. High activity of carbon nanotubes supported binary and ternary Pd-based catalysts for methanol, ethanol and formic acid electro-oxidation

    NASA Astrophysics Data System (ADS)

    Zhu, Fuchun; Ma, Guanshui; Bai, Zhongchao; Hang, Ruiqiang; Tang, Bin; Zhang, Zhonghua; Wang, Xiaoguang

    2013-11-01

    In this study, we have synthesized a series of multi-walled carbon nanotubes supported Pd, PdCu(molar ratio 1:1), PdSn(1:1) and PdCuSn(1:1:1) catalysts by chemical reduction with NaBH4 as a reducing agent. These catalysts are characterized using X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry and chronoamperometry. During the potential cycling activation, it is found that the additive Cu is prone to suffer leaching while the dissolution of Sn rarely occurs. Electrochemical measurements demonstrate that, the co-alloying of Pd with Cu and Sn can trigger the best catalytic activity enhancement as compared with the binary PdCu/CNTs, PdSn/CNTs and mono-component Pd/CNTs catalysts. The PdCuSn/CNTs reveals the most excellent activities toward methanol, ethanol and formic acid electro-oxidation and the corresponding mass activity can attain to 395.94, 872.70 and 534.83 mA mg-1 Pd, respectively. The possible promotion effect of additive Sn or/and Cu on the electrocatalytic activity improvement is also analyzed.

  16. Quantum free energy landscapes from ab initio path integral metadynamics: Double proton transfer in the formic acid dimer is concerted but not correlated

    SciTech Connect

    Ivanov, Sergei D. Grant, Ian M.; Marx, Dominik

    2015-09-28

    With the goal of computing quantum free energy landscapes of reactive (bio)chemical systems in multi-dimensional space, we combine the metadynamics technique for sampling potential energy surfaces with the ab initio path integral approach to treating nuclear quantum motion. This unified method is applied to the double proton transfer process in the formic acid dimer (FAD), in order to study the nuclear quantum effects at finite temperatures without imposing a one-dimensional reaction coordinate or reducing the dimensionality. Importantly, the ab initio path integral metadynamics technique allows one to treat the hydrogen bonds and concomitant proton transfers in FAD strictly independently and thus provides direct access to the much discussed issue of whether the double proton transfer proceeds via a stepwise or concerted mechanism. The quantum free energy landscape we compute for this H-bonded molecular complex reveals that the two protons move in a concerted fashion from initial to product state, yet world-line analysis of the quantum correlations demonstrates that the protons are as quantum-uncorrelated at the transition state as they are when close to the equilibrium structure.

  17. Quantum free energy landscapes from ab initio path integral metadynamics: Double proton transfer in the formic acid dimer is concerted but not correlated

    NASA Astrophysics Data System (ADS)

    Ivanov, Sergei D.; Grant, Ian M.; Marx, Dominik

    2015-09-01

    With the goal of computing quantum free energy landscapes of reactive (bio)chemical systems in multi-dimensional space, we combine the metadynamics technique for sampling potential energy surfaces with the ab initio path integral approach to treating nuclear quantum motion. This unified method is applied to the double proton transfer process in the formic acid dimer (FAD), in order to study the nuclear quantum effects at finite temperatures without imposing a one-dimensional reaction coordinate or reducing the dimensionality. Importantly, the ab initio path integral metadynamics technique allows one to treat the hydrogen bonds and concomitant proton transfers in FAD strictly independently and thus provides direct access to the much discussed issue of whether the double proton transfer proceeds via a stepwise or concerted mechanism. The quantum free energy landscape we compute for this H-bonded molecular complex reveals that the two protons move in a concerted fashion from initial to product state, yet world-line analysis of the quantum correlations demonstrates that the protons are as quantum-uncorrelated at the transition state as they are when close to the equilibrium structure.

  18. Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation.

    PubMed

    Lee, Dong-Wook; Jin, Min-Ho; Lee, Young-Joo; Park, Ju-Hyoung; Lee, Chun-Boo; Park, Jong-Soo

    2016-01-01

    The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method. PMID:27198855

  19. Hydrogen production from formic acid solution by modified TiO2 and titanate nanotubes in a two-step system under visible light irradiation.

    PubMed

    Yeh, H M; Lo, S L; Chen, M J; Chen, H Y

    2014-01-01

    Hydrogen gas is one of the most promising renewable energy sources, and the final product of hydrogen combustion is nothing but water. However, it is still a big challenge to produce hydrogen and store it. Many studies have been conducted into produce hydrogen from water using photocatalysts. Z-scheme photocatalysis is a two-photocatalyst system that comprises a hydrogen catalyst and an oxygen catalyst to produce hydrogen and oxygen respectively. Compared to the one-step system, the two-step system can promote the efficiency of water splitting. In addition, formic acid (FA) is a convenient hydrogen-storage material and can be safely handled in aqueous solutions. Therefore, this study investigated the photocatalytic conversion of FA solution to hydrogen using visible light with several types of hydrogen catalysts (CdS/titanate nanotubes (TNTs), CdS/TiO2, Pt/CdS/TNTs) and WO3 as the oxygen catalyst. The results showed that the yield of hydrogen with CdS/TNTs + WO3 was much higher than with CdS/TiO2 + WO3. Moreover, coating the photocatalysts with metal could further promote the reaction. The optimal platinum loading was 0.01 wt%, and the hydrogen production achieved was 852.5 μmol · h(-1) with 20 vol% FA solution. PMID:24759528

  20. On the validity of the basis set superposition error and complete basis set limit extrapolations for the binding energy of the formic acid dimer

    SciTech Connect

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2015-03-07

    We report the variation of the binding energy of the formic acid dimer at the CCSD(T)/ Complete Basis Set limit and examine the validity of the BSSE-correction, previously challenged by Kalescky, Kraka and Cremer [J. Chem. Phys. 140 (2014) 084315]. Our best estimate of D0=14.3±0.1 kcal/mol is in excellent agreement with the experimental value of 14.22±0.12 kcal/mol. The BSSE correction is indeed valid for this system since it exhibits the expected behavior of decreasing with increasing basis set size and its inclusion produces the same limit (within 0.1 kcal/mol) as the one obtained from extrapolation of the uncorrected binding energy. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. A portion of this research was performed using the Molecular Science Computing Facility (MSCF) in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.

  1. Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

    NASA Astrophysics Data System (ADS)

    Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2015-12-01

    Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53-75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol at a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.

  2. Highly active carbon supported palladium catalysts decorated by a trace amount of platinum by an in-situ galvanic displacement reaction for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Li, Zuopeng; Li, Muwu; Han, Mingjia; Wu, Xin; Guo, Yong; Zeng, Jianhuang; Li, Yuexia; Liao, Shijun

    2015-03-01

    Aimed at reducing platinum usage and improved catalytic activity for formic acid oxidation, a series of Pt decorated Pd/C catalysts are prepared by an in-situ galvanic displacement reaction between freshly prepared Pd/C ink and H2PtCl6 in an aqueous solution. The catalysts with 4 nm particle sizes and 20 wt.% loadings have been characterized by transmission electron microscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy (XPS). The electrochemical evaluations by cyclic voltammetry are conducted to test out the CO tolerance and catalytic activities. In addition to XPS analysis, a theoretical calculation has been attempted the first time to find out the surface Pd/Pt molar ratios. The decay rate of the catalysts has been evaluated by the percentage of the forward/backward peak current retained using the value at the 20th cycle divided by that in the first cycle. Compared with a Pd/C benchmark, all Pt decorated Pd/C register enhanced activity while the cost remains virtually unchanged. The optimized catalyst is found to have a Pd/Pt molar ratio of 75:1 but with 2.5 times activity relative to that of Pd/C.

  3. Kinetic study of formic acid degradation by Fe3+ doped TiO2 self-cleaning nanostructure surfaces prepared by cold spray

    NASA Astrophysics Data System (ADS)

    Sayyar, Zahra; Akbar Babaluo, Ali; Shahrouzi, Javad Rahbar

    2015-04-01

    A self-cleaning solution was introduced in this paper based on sol-gel and was applied for preparing self-cleaning TiO2. Fe3+ ions have been doped into the TiO2 crystal lattice. XRD analysis indicated that the obtained TiO2 powder contains mainly the anatase phase and TiO2 powder has a crystallite size distribution of 10-12 nm. SEM micrographs have also confirmed nanometric distribution of the obtained powder. A series of uniform and transparent TiO2 and Fe/TiO2 films were prepared by cold spray technique which may result in high uniformity in the final coated surfaces. Photocatalytic activity of the thin films was investigated through degradation of aqueous formic acid under UV-visible light. The Langmuir-Hinshelwood kinetic model was used to interpret quantitatively the observed kinetic experimental result. Comparative study of the obtained coated surfaces with those of uncoated surfaces, demonstrated a remarkable performance. The Fe/TiO2 films and their calcination at 650 °C demonstrated the highest photocatalytic activity.

  4. Adsorption of formic acid on rutile TiO{sub 2} (110) revisited: An infrared reflection-absorption spectroscopy and density functional theory study

    SciTech Connect

    Mattsson, A.; Österlund, L.; Hu, Shuanglin Hermansson, K.

    2014-01-21

    Formic acid (HCOOH) adsorption on rutile TiO{sub 2} (110) has been studied by s- and p-polarized infrared reflection-absorption spectroscopy (IRRAS) and spin-polarized density functional theory together with Hubbard U contributions (DFT+U) calculations. To compare with IRRAS spectra, the results from the DFT+U calculations were used to simulate IR spectra by employing a three-layer model, where the adsorbate layer was modelled using Lorentz oscillators with calculated dielectric constants. To account for the experimental observations, four possible formate adsorption geometries were calculated, describing both the perfect (110) surface, and surfaces with defects; either O vacancies or hydroxyls. The majority species seen in IRRAS was confirmed to be the bridging bidentate formate species with associated symmetric and asymmetric frequencies of the ν(OCO) modes measured to be at 1359 cm{sup −1} and 1534 cm{sup −1}, respectively. The in-plane δ(C–H) wagging mode of this species couples to both the tangential and the normal component of the incident p-polarized light, which results in absorption and emission bands at 1374 cm{sup −1} and 1388 cm{sup −1}. IRRAS spectra measured on surfaces prepared to be either reduced, stoichiometric, or to contain surplus O adatoms, were found to be very similar. By comparisons with computed spectra, it is proposed that in our experiments, formate binds as a minority species to an in-plane Ti{sub 5c} atom and a hydroxyl, rather than to O vacancy sites, the latter to a large extent being healed even at our UHV conditions. Excellent agreement between calculated and experimental IRRAS spectra is obtained. The results emphasize the importance of protonation and reactive surface hydroxyls – even under UHV conditions – as reactive sites in e.g., catalytic applications.

  5. On the validity of the basis set superposition error and complete basis set limit extrapolations for the binding energy of the formic acid dimer

    SciTech Connect

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2015-03-07

    We report the variation of the binding energy of the Formic Acid Dimer with the size of the basis set at the Coupled Cluster with iterative Singles, Doubles and perturbatively connected Triple replacements [CCSD(T)] level of theory, estimate the Complete Basis Set (CBS) limit, and examine the validity of the Basis Set Superposition Error (BSSE)-correction for this quantity that was previously challenged by Kalescky, Kraka, and Cremer (KKC) [J. Chem. Phys. 140, 084315 (2014)]. Our results indicate that the BSSE correction, including terms that account for the substantial geometry change of the monomers due to the formation of two strong hydrogen bonds in the dimer, is indeed valid for obtaining accurate estimates for the binding energy of this system as it exhibits the expected decrease with increasing basis set size. We attribute the discrepancy between our current results and those of KKC to their use of a valence basis set in conjunction with the correlation of all electrons (i.e., including the 1s of C and O). We further show that the use of a core-valence set in conjunction with all electron correlation converges faster to the CBS limit as the BSSE correction is less than half than the valence electron/valence basis set case. The uncorrected and BSSE-corrected binding energies were found to produce the same (within 0.1 kcal/mol) CBS limits. We obtain CCSD(T)/CBS best estimates for D{sub e} = − 16.1 ± 0.1 kcal/mol and for D{sub 0} = − 14.3 ± 0.1 kcal/mol, the later in excellent agreement with the experimental value of −14.22 ± 0.12 kcal/mol.

  6. Tropospheric Emission Spectrometer (TES) satellite observations of ammonia, methanol, formic acid, and carbon monoxide over the Canadian oil sands: validation and model evaluation

    NASA Astrophysics Data System (ADS)

    Shephard, M. W.; McLinden, C. A.; Cady-Pereira, K. E.; Luo, M.; Moussa, S. G.; Leithead, A.; Liggio, J.; Staebler, R. M.; Akingunola, A.; Makar, P.; Lehr, P.; Zhang, J.; Henze, D. K.; Millet, D. B.; Bash, J. O.; Zhu, L.; Wells, K. C.; Capps, S. L.; Chaliyakunnel, S.; Gordon, M.; Hayden, K.; Brook, J. R.; Wolde, M.; Li, S.-M.

    2015-12-01

    The wealth of air quality information provided by satellite infrared observations of ammonia (NH3), carbon monoxide (CO), formic acid (HCOOH), and methanol (CH3OH) is currently being explored and used for a number of applications, especially at regional or global scales. These applications include air quality monitoring, trend analysis, emissions, and model evaluation. This study provides one of the first direct validations of Tropospheric Emission Spectrometer (TES) satellite-retrieved profiles of NH3, CH3OH, and HCOOH through comparisons with coincident aircraft profiles. The comparisons are performed over the Canadian oil sands region during the intensive field campaign (August-September, 2013) in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring (JOSM). The satellite/aircraft comparisons over this region during this period produced errors of (i) +0.08 ± 0.25 ppbv for NH3, (ii) +7.5 ± 23 ppbv for CO, (iii) +0.19 ± 0.46 ppbv for HCOOH, and (iv) -1.1 ± 0.39 ppbv for CH3OH. These values mostly agree with previously estimated retrieval errors; however, the relatively large negative bias in CH3OH and the significantly greater positive bias for larger HCOOH and CO values observed during this study warrant further investigation. Satellite and aircraft ammonia observations during the field campaign are also used in an initial effort to perform preliminary evaluations of Environment Canada's Global Environmental Multi-scale - Modelling Air quality and CHemistry (GEM-MACH) air quality modelling system at high resolution (2.5 × 2.5 km2). These initial results indicate a model underprediction of ~ 0.6 ppbv (~ 60 %) for NH3, during the field campaign period. The TES/model CO comparison differences are ~ +20 ppbv (~ +20 %), but given that under these conditions the TES/aircraft comparisons also show a small positive TES CO bias indicates that the overall model underprediction of CO is closer to ~ 10 % at 681 hPa (~ 3 km) during this period.

  7. A search for formic acid in the upper troposphere - A tentative identification of the 1105-per cm nu-6 band Q branch in high-resolution balloon-borne solar absorption spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. H.; Murcray, D. G.; Rinsland, C. P.

    1984-01-01

    Infrared solar absorption spectra recorded at 0.02-per cm resolution during a balloon flight from Alamogordo, NM (33 deg N), on March 23, 1981, have been analyzed for the possible presence of absorption by formic acid (HCOOH). An absorption feature at 1105 per cm has been tentatively identified in upper tropospheric spectra as due to the nu-6 band Q branch. A preliminary analysis indicates a concentration of about 0.6 ppbv and 0.4 ppbv near 8 and 10 km, respectively.

  8. A Search for Formic Acid in the Upper Troposphere: A Tentative Identification of the 1105-cm(exp -1) nu(sub 6) Band Q Branch in High-Resolution Balloon-Borne Solar Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. H.; Murcray, D. G.; Rinsland, C. P.

    1984-01-01

    Infrared solar absorption spectra recorded at 0.02/cm resolution during a balloon flight from Alamogordo, N.M. (33 deg N), on March 23, 1981, have been analyzed for the possible presence of absorption by formic acid (HCOOH). An absorption feature at 1105/ cm has been tentatively identified in upper tropospheric spectra as due to the nu(sub 6) band Q branch. A preliminary analysis indicates a concentration of approx. = 0.6 ppbv and approx. = 0.4 ppbv near 8 and 10 km, respectively.

  9. Inverse metabolic engineering based on transient acclimation of yeast improves acid-containing xylose fermentation and tolerance to formic and acetic acids.

    PubMed

    Hasunuma, Tomohisa; Sakamoto, Takatoshi; Kondo, Akihiko

    2016-01-01

    Improving the production of ethanol from xylose is an important goal in metabolic engineering of Saccharomyces cerevisiae. Furthermore, S. cerevisiae must produce ethanol in the presence of weak acids (formate and acetate) generated during pre-treatment of lignocellulosic biomass. In this study, weak acid-containing xylose fermentation was significantly improved using cells that were acclimated to the weak acids during pre-cultivation. Transcriptome analyses showed that levels of transcripts for transcriptional/translational machinery-related genes (RTC3 and ANB1) were enhanced by formate and acetate acclimation. Recombinant yeast strains overexpressing RTC3 and ANB1 demonstrated improved ethanol production from xylose in the presence of the weak acids, along with improved tolerance to the acids. Novel metabolic engineering strategy based on the combination of short-term acclimation and system-wide analysis was developed, which can develop stress-tolerant strains in a short period of time, although conventional evolutionary engineering approach has required long periods of time to isolate inhibitor-adapted strains. PMID:26521247

  10. Heart Birth Defects Dropped After Folic Acid Was Added to Food

    MedlinePlus

    ... 160673.html Heart Birth Defects Dropped After Folic Acid Was Added to Food Canadian study found that ... 29, 2016 (HealthDay News) -- The introduction of folic acid-fortified foods in Canada was associated with a ...

  11. Oil Biotechnology: Value-Added Products and Bioactive Fatty Acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    During my 40+ years research career, I have been working on "biocatalysis" of hydrophobic organic compounds, both petroleum oil and vegetable oil, to convert them to value-added products. "Biocatalysis" is defined as the use of a biocatalyst such as whole microbial cells or enzymes, in an aqueous o...

  12. Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air.

    PubMed

    Coelho, Lúcia H G; Melchert, Wanessa R; Rocha, Flavio R; Rocha, Fábio R P; Gutz, Ivano G R

    2010-11-15

    The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the μg m(-3) range) and their variations with sampling site and time. In this work, a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE), a quick separation technique that requires nothing more than some nanoliters of sample and, when combined with capacitively coupled contactless conductometric detection (C(4)D), is particularly favorable for ionic species that do not absorb in the UV-vis region, like the target analytes formaldehyde, formic acid, acetic acid and ammonium. The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry's constant such as formaldehyde and carboxylic acids, or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8.3 nL s(-1)), while the sample was aspirated through the annular gap of the concentric tubes at 2.5 mL s(-1). A second unit, in all similar to the CMDS, was operated as a capillary membrane diffusion emitter (CMDE), generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS. The fluids of the system were driven with inexpensive aquarium air pumps, and the collected samples were stored in vials cooled by a Peltier element. Complete protocols were developed for the analysis, in air, of NH(3), CH(3)COOH, HCOOH and, with a derivatization setup, CH(2)O, by associating the CMDS collection with the determination by CE-C(4)D. The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot's reaction. Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction, solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW). All

  13. Production of Value-added Products by Lactic Acid Bacteria

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lactic acid bacteria (LAB) are a group of facultative anaerobic, catalase negative, nonmotile and nonsporeforming–Gram positive bacteria. Most LAB utilize high energy C sources including monomer sugars to produce energy to maintain cellular structure and function. This anaerobic fermentation proce...

  14. Estimating the acidity of transition metal hydride and dihydrogen complexes by adding ligand acidity constants.

    PubMed

    Morris, Robert H

    2014-02-01

    A simple equation (pKa(THF) = ∑AL + Ccharge + Cnd + Cd6) can be used to obtain an estimate of the pKa of diamagnetic transition metal hydride and dihydrogen complexes in tetrahydrofuran, and, by use of conversion equations, in other solvents. It involves adding acidity constants AL for each of the ligands in the 5-, 6-, 7-, or 8-coordinate conjugate base complex of the hydride or dihydrogen complex along with a correction for the charge (Ccharge = -15, 0 or 30 for x = +1, 0 or -1 charge, respectively) and the periodic row of the transition metal (Cnd = 0 for 3d or 4d metal, 2 for 5d metal) as well as a correction for d(6) octahedral acids (Cd6 = 6 for d(6) metal ion in the acid, 0 for others) that are not dihydrogen complexes. Constants AL are provided for 13 commonly occurring ligand types; of these, nine neutral ligands are correlated with Lever's electrochemical ligand parameters EL. This method gives good estimates of the over 170 literature pKa values that range from less than zero to 50 with a standard deviation of 3 pKa units for complexes of the metals chromium to nickel, molybdenum, ruthenium to palladium, and tungsten to platinum in the periodic table. This approach allows a quick assessment of the acidity of hydride complexes found in nature (e.g., hydrogenases) and in industry (e.g., catalysis and hydrogen energy applications). The pKa values calculated for acids that have bulky or large bite angle chelating ligands deviate the most from this correlation. The method also provides an estimate of the base strength of the deprotonated form of the complex. PMID:24410025

  15. ADS genes for reducing saturated fatty acid levels in seed oils

    DOEpatents

    Heilmann, Ingo H.; Shanklin, John

    2010-02-02

    The present invention relates to enzymes involved in lipid metabolism. In particular, the present invention provides coding sequences for Arabidopsis Desaturases (ADS), the encoded ADS polypeptides, and methods for using the sequences and encoded polypeptides, where such methods include decreasing and increasing saturated fatty acid content in plant seed oils.

  16. ADS genes for reducing saturated fatty acid levels in seed oils

    DOEpatents

    Heilmann, Ingo H; Shanklin, John

    2014-03-18

    The present invention relates to enzymes involved in lipid metabolism. In particular, the present invention provides coding sequences for Arabidopsis Desaturases (ADS), the encoded ADS polypeptides, and methods for using the sequences and encoded polypeptides, where such methods include decreasing and increasing saturated fatty acid content in plant seed oils.

  17. Utilisation of single added fatty acids by consortia of digester sludge in batch culture

    SciTech Connect

    Wagner, Andreas Otto; Gstrauntaler, Gudrun; Illmer, Paul

    2010-10-15

    Inocula derived from an anaerobic digester were used to study (i) their potential for methane production and (ii) the utilisation rates of different short chain fatty acids (SCFAs) by the microbial community in defined media with mono-carbon sources (formic-, acetetic-, propionic-, butyric acid) in batch culture. It could be demonstrated that the microbial reactor population could be transferred successfully to the lab, and its ability to build up methane was present even with deteriorating biogas plant performance. Therefore, this reduction in performance of the biogas plant was not due to a decrease in abundance, but due to an inactivity of the microbial community. Generally, the physico-chemical properties of the biogas plant seemed to favour hydrogenotrophic methanogens, as seen by the high metabolisation rates of formate compared with all other carbon sources. In contrast, acetoclastic methanogenesis could be shown to play a minor role in the methane production of the investigated biogas plant, although the origin of up to 66% of methane is generally suggested to be generated through acetoclastic pathway.

  18. Short-fiber protein of ad40 confers enteric tropism and protection against acidic gastrointestinal conditions.

    PubMed

    Rodríguez, Ester; Romero, Carolina; Río, Adolfo; Miralles, Marta; Raventós, Aida; Planells, Laura; Burgueño, Joan F; Hamada, Hirofumi; Perales, Jose Carlos; Bosch, Assumpció; Gassull, Miguel Angel; Fernández, Ester; Chillon, Miguel

    2013-08-01

    The lack of vectors for selective gene delivery to the intestine has hampered the development of gene therapy strategies for intestinal diseases. We hypothesized that chimeric adenoviruses of Ad5 (species C) displaying proteins of the naturally enteric Ad40 (species F) might hold the intestinal tropism of the species F and thus be useful for gene delivery to the intestine. As oral-fecal dissemination of enteric adenovirus must withstand the conditions encountered in the gastrointestinal tract, we studied the resistance of chimeric Ad5 carrying the short-fiber protein of Ad40 to acid milieu and proteases and found that the Ad40 short fiber confers resistance to inactivation in acidic conditions and that AdF/40S was further activated upon exposure to low pH. In contrast, the chimeric AdF/40S exhibited only a slightly higher protease resistance compared with Ad5 to proteases present in simulated gastric juice. Then, the biodistribution of different chimeric adenoviruses by oral, rectal, and intravenous routes was tested. Expression of reporter β-galactosidase was measured in extracts of 15 different organs 3 days after administration. Our results indicate that among the chimeric viruses, only intrarectally given AdF/40S infected the colon (preferentially enteroendocrine cells and macrophages) and to a lesser extent, the small intestine, whereas Ad5 infectivity was very poor in all tissues. Additional in vitro experiments showed improved infectivity of AdF/40S also in different human epithelial cell lines. Therefore, our results point at the chimeric adenovirus AdF/40S as an interesting vector for selective gene delivery to treat intestinal diseases. PMID:23746215

  19. Omega-3 fatty acid docosahexaenoic acid increases SorLA/LR11, a sorting protein with reduced expression in sporadic Alzheimer's disease (AD): relevance to AD prevention.

    PubMed

    Ma, Qiu-Lan; Teter, Bruce; Ubeda, Oliver J; Morihara, Takashi; Dhoot, Dilsher; Nyby, Michael D; Tuck, Michael L; Frautschy, Sally A; Cole, Greg M

    2007-12-26

    Environmental and genetic factors, notably ApoE4, contribute to the etiology of late-onset Alzheimer's disease (LOAD). Reduced mRNA and protein for an apolipoprotein E (ApoE) receptor family member, SorLA (LR11) has been found in LOAD but not early-onset AD, suggesting that LR11 loss is not secondary to pathology. LR11 is a neuronal sorting protein that reduces amyloid precursor protein (APP) trafficking to secretases that generate beta-amyloid (Abeta). Genetic polymorphisms that reduce LR11 expression are associated with increased AD risk. However these polymorphisms account for only a fraction of cases with LR11 deficits, suggesting involvement of environmental factors. Because lipoprotein receptors are typically lipid-regulated, we postulated that LR11 is regulated by docosahexaenoic acid (DHA), an essential omega-3 fatty acid related to reduced AD risk and reduced Abeta accumulation. In this study, we report that DHA significantly increases LR11 in multiple systems, including primary rat neurons, aged non-Tg mice and an aged DHA-depleted APPsw AD mouse model. DHA also increased LR11 in a human neuronal line. In vivo elevation of LR11 was also observed with dietary fish oil in young rats with insulin resistance, a model for type II diabetes, another AD risk factor. These data argue that DHA induction of LR11 does not require DHA-depleting diets and is not age dependent. Because reduced LR11 is known to increase Abeta production and may be a significant genetic cause of LOAD, our results indicate that DHA increases in SorLA/LR11 levels may play an important role in preventing LOAD. PMID:18160637

  20. Synthesis of the A-D Ring System of the Gambieric Acids.

    PubMed

    Clark, J Stephen; Romiti, Filippo; Sieng, Bora; Paterson, Laura C; Stewart, Alister; Chaudhury, Subhabrata; Thomas, Lynne H

    2015-10-01

    The A-D fragment of gambieric acids A and C has been synthesized using an asymmetric Tsuji-Trost allylation reaction to couple the two key segments. The A ring fragment has been prepared by a short and highly efficient route involving diastereoselective Lewis acid mediated alkylation of an acetal. Iterative ring-closing metathesis reactions have been used to construct cyclic ethers and assemble the tricyclic B-D fragment. PMID:26367818

  1. ACID DEPOSITION SYSTEM (ADS) FOR STATISTICAL REPORTING: SYSTEM DESIGN AND USER'S CODE MANUAL

    EPA Science Inventory

    This document is a general purpose description of the ADS data management system. It explains to acid precipitation monitoring network managers how their data is being merged with that from other networks. For the researcher, this document defines what information is available in...

  2. Comparison of Buffer Effect of Different Acids During Sandstone Acidizing

    NASA Astrophysics Data System (ADS)

    Umer Shafiq, Mian; Khaled Ben Mahmud, Hisham; Hamid, Mohamed Ali

    2015-04-01

    The most important concern of sandstone matrix acidizing is to increase the formation permeability by removing the silica particles. To accomplish this, the mud acid (HF: HCl) has been utilized successfully for many years to stimulate the sandstone formations, but still it has many complexities. This paper presents the results of laboratory investigations of different acid combinations (HF: HCl, HF: H3PO4 and HF: HCOOH). Hydrofluoric acid and fluoboric acid are used to dissolve clays and feldspar. Phosphoric and formic acids are added as a buffer to maintain the pH of the solution; also it allows the maximum penetration of acid into the core sample. Different tests have been performed on the core samples before and after the acidizing to do the comparative study on the buffer effect of these acids. The analysis consists of permeability, porosity, color change and pH value tests. There is more increase in permeability and porosity while less change in pH when phosphoric and formic acids were used compared to mud acid. From these results it has been found that the buffer effect of phosphoric acid and formic acid is better than hydrochloric acid.

  3. [Progress in engineering Escherichia coli for production of high-value added organic acids and alcohols].

    PubMed

    Wang, Jiming; Liu, Wei; Xu, Xin; Zhang, Haibo; Xian, Mo

    2013-10-01

    Confronted with the gradual exhaustion of the earth's fossil energy resources and the grimmer environmental deterioration, the bio-based process to produce high-value added platform chemicals from renewable biomass is attracting growing interest. Escherichia coli has been chosen as a workhouse for the production of many valuable chemicals due to various advantages, such as clear genetic background, convenient to be genetically modified and good growth properties with low nutrient requirements. Rational strain development of E. coli achieved by metabolic engineering strategies has provided new processes for efficiently biotechnological production of various high-value chemical building blocks. This review focuses on recent progresses in metabolic engineering of E. coli that lead to efficient recombinant biocatalysts for production of high-value organic acids such as succinic acid, 3-hydroxypropanoic acid and glucaric acid as well as alcohols like glycerol and xylitol. Besides, this review also discusses several other platform chemicals, including 2,5-furan dicarboxylic acid, aspartic acid, glutamic acid, itaconic acid, levulinic acid, 3-hydroxy-gamma-butyrolactone and sorbitol, which have not been produced by E. coli until now. PMID:24432652

  4. Bioavailability of iron, vitamin A, zinc, and folic acid when added to condiments and seasonings.

    PubMed

    Degerud, Eirik M; Manger, Mari Skar; Strand, Tor A; Dierkes, Jutta

    2015-11-01

    Seasonings and condiments can be candidate vehicles for micronutrient fortification if consumed consistently and if dietary practices ensure bioavailability of the nutrient. In this review, we identify factors that may affect the bioavailability of iron, vitamin A, zinc, and folic acid when added to seasonings and condiments and evaluate their effects on micronutrient status. We take into consideration the chemical and physical properties of different forms of the micronutrients, the influence of the physical and chemical properties of foods and meals to which fortified seasonings and condiments are typically added, and interactions between micronutrients and the physiological and nutritional status of the target population. Bioavailable fortificants of iron have been developed for use in dry or fluid vehicles. For example, sodium iron ethylenediaminetetraacetic acid (NaFeEDTA) and ferrous sulfate with citric acid are options for iron fortification of fish and soy sauce. Furthermore, NaFeEDTA, microencapsulated ferrous fumarate, and micronized elemental iron are potential fortificants in curry powder and salt. Dry forms of retinyl acetate or palmitate are bioavailable fortificants of vitamin A in dry candidate vehicles, but there are no published studies of these fortificants in fluid vehicles. Studies of zinc and folic acid bioavailability in seasonings and condiments are also lacking. PMID:26469774

  5. Composition and Fatty Acid Profile of Goat Meat Sausages with Added Rice Bran

    PubMed Central

    Gebrelul, Sebhatu

    2014-01-01

    A scientific consensus on the relationship between obesity, obesity related diseases, and diet has emerged. One of the factors is overconsumption of the red meats such as pork and beef. Goat meat has the potential to replace these traditionally consumed meats. Rice bran is a rich source of antioxidants such as vitamin E. In this study, goat meat sausages were formulated to contain 0, 1.5 or 3 percent stabilized rice bran. Proximate and fatty acid composition, α-tocopherol, cholesterol concentration, and antioxidant activities of cooked goat meat sausages containing varying percentages of rice bran were measured. Data were analyzed using a fixed effects model. The fat percentage in the goat meat sausages increased in response to increasing rice bran percentages (P < 0.001). Saturated fatty acids concentration decreased linearly (P < 0.01), while unsaturated fatty acids and omega-3 and omega-6 fatty acids increased linearly in response to increasing rice bran percentages (P < 0.05). The concentration of α-tocopherol in sausages increased linearly in response to increasing rice bran percentages (P < 0.01). Also, antioxidant activity increased linearly in sausages in response to added rice bran (P < 0.01). The cholesterol concentration of sausages did not vary significantly in response to added rice bran. PMID:26904643

  6. Growth of Thiobacillus ferrooxidans on formic acid

    SciTech Connect

    Pronk, J.T.; Meijer, W.M.; Hazeu, W.; vanDijken, J.P.; Bos, P.; Kuenen, J.G. )

    1991-07-01

    A variety of acidophilic microorganisms were shown to be capable of oxidizing formate. These included Thiobacillus ferrooxidans ATCC 21834, which, however, could not grow on formate in normal batch cultures. However, the organism could be grown on formate when the substrate supply was growth limiting, e.g., in formate-limited chemostat cultures. The cell densities achieved by the use of the latter cultivation method were higher than cell densities reported for growth of T. ferrooxidans on ferrous iron or reduced sulfur compounds. Inhibition of formate oxidation by cell suspensions, but not cell extracts, of formate-grown T. ferrooxidans occurred at formate concentrations above 100 {mu}M. This observation explains the inability of the organism to grow on formate in batch cultures. Cells grown in formate-limited chemostat cultures retained the ability to oxidize ferrous iron at high rates. Ribulose 1,5-bisphosphate carboxylase activities in cell extracts indicated that T. ferrooxidans employs the Calvin cycle for carbon assimilation during growth on formate. Oxidation of formate by cell extracts was NAD(P) independent.

  7. Adding an appropriate amino acid during crosslinking results in more stable crosslinked enzyme aggregates.

    PubMed

    Mukherjee, Joyeeta; Majumder, Abir Baran; Gupta, Munishwar Nath

    2016-08-15

    Carrier free immobilization, especially crosslinked enzyme aggregates (CLEAs), has become an important design for biocatalysis in several areas. Adding amino acids during formation of CLEAs was found to give biocatalysts more stable at 55 °C and in the presence of 60% acetonitrile. The half-lives of CLEAs prepared with and without Arg addition were 21 and 15 h (subtilisin) and 4 and 1.6 h (α-chymotrypsin) at 55 °C, respectively. The corresponding half-lives during acetonitrile presence were 4.1 and 3.0 h (subtilisin) and 39 and 22 min (α-chymotrypsin), respectively. CLEAs made with Arg had higher percentages of alpha helix. CLEAs made by adding Lys, Ala, or Asp also were more stable. In the case of Thermomyces lanuginosus lipase (TLL), CLEA with Ala was even more stable than CLEA with Arg. The addition of a suitable amino acid, thus, enhances CLEA stabilities. The results are discussed in the light of earlier results on chemical modification of proteins and the observation that the Arg/Lys ratio is invariably high in the case of enzymes from thermophiles. PMID:27237371

  8. SULFUR CHEMISTRY. Gas phase observation and microwave spectroscopic characterization of formic sulfuric anhydride.

    PubMed

    Mackenzie, Rebecca B; Dewberry, Christopher T; Leopold, Kenneth R

    2015-07-01

    We report the observation of a covalently bound species, formic sulfuric anhydride (FSA), that is produced from formic acid and sulfur trioxide under supersonic jet conditions. FSA has been structurally characterized by means of microwave spectroscopy and further investigated by using density functional theory and ab initio calculations. Theory indicates that a π2 + π2 + σ2 cycloaddition reaction between SO3 and HCOOH is a plausible pathway to FSA formation and that such a mechanism would be effectively barrierless. We speculate on the possible role that FSA may play in the Earth's atmosphere. PMID:26138972

  9. Intake of Added Sugar and Sugar-Sweetened Drink and Serum Uric Acid Concentration in US Men and Women

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fructose-induced hyperuricemia might have a causal role in metabolic syndrome, hypertension, and other chronic disease. However, no study has investigated whether sugar added to foods or sugar-sweetened beverages, which are major sources of fructose, are associated with serum uric acid concentration...

  10. Lipid and fatty acid metabolism in Ralstonia eutropha: relevance for the biotechnological production of value-added products.

    PubMed

    Riedel, Sebastian L; Lu, Jingnan; Stahl, Ulf; Brigham, Christopher J

    2014-02-01

    Lipid and fatty acid metabolism has been well studied in model microbial organisms like Escherichia coli and Bacillus subtilis. The major precursor of fatty acid biosynthesis is also the major product of fatty acid degradation (β-oxidation), acetyl-CoA, which is a key metabolite for all organisms. Controlling carbon flux to fatty acid biosynthesis and from β-oxidation allows for the biosynthesis of natural products of biotechnological importance. Ralstonia eutropha can utilize acetyl-CoA from fatty acid metabolism to produce intracellular polyhydroxyalkanoate (PHA). R. eutropha can also be engineered to utilize fatty acid metabolism intermediates to produce different PHA precursors. Metabolism of lipids and fatty acids can be rerouted to convert carbon into other value-added compounds like biofuels. This review discusses the lipid and fatty acid metabolic pathways in R. eutropha and how they can be used to construct reagents for the biosynthesis of products of industrial importance. Specifically, how the use of lipids or fatty acids as the sole carbon source in R. eutropha cultures adds value to these biotechnological products will be discussed here. PMID:24343766

  11. Treatment of Alzheimer's disease with anti-homocysteic acid antibody in 3xTg-AD male mice.

    PubMed

    Hasegawa, Tohru; Mikoda, Nobuyuki; Kitazawa, Masashi; LaFerla, Frank M

    2010-01-01

    Alzheimer's disease (AD) is an age-associated progressive neurodegenerative disorder with dementia, the exact pathogenic mechanisms of which remain unknown. We previously reported that homocysteic acid (HA) may be one of the pathological biomarkers in the brain with AD and that the increased levels of HA may induce the accumulation of intraneuronal amyloid-beta (Abeta) peptides. In this study, we further investigated the pathological role of HA in a mouse model of AD. Four-month-old prepathological 3xTg-AD mice exhibited higher levels of HA in the hippocampus than did age-matched nontransgenic mice, suggesting that HA accumulation may precede both Abeta and tau pathologies. We then fed 3-month-old 3xTg-AD mice with vitamin B6-deficient food for 3 weeks to increase the HA levels in the brain. Concomitantly, mice received either saline or anti-HA antibody intraventricularly via a guide cannula every 3 days during the course of the B6-deficient diet. We found that mice that received anti-HA antibody significantly resisted cognitive impairment induced by vitamin B6 deficiency and that AD-related pathological changes in their brains was attenuated compared with the saline-injected control group. A similar neuroprotective effect was observed in 12-month-old 3xTg-AD mice that received anti-HA antibody injections while receiving the regular diet. We conclude that increased brain HA triggers memory impairment and that this condition deteriorates with amyloid and leads to subsequent neurodegeneration in mouse models of AD. PMID:20098691

  12. Electrochemical activity of iron in acid treated bentonite and influence of added nickel

    NASA Astrophysics Data System (ADS)

    Mudrinić, T.; Mojović, Z.; Milutinović-Nikolić, A.; Mojović, M.; Žunić, M.; Vukelić, N.; Jovanović, D.

    2015-10-01

    Bentonite originated from Mečji Do, Serbia, was submitted to acid treatment at 70 °C for 30 min, while only the concentration of applied HCl varied. The obtained acid treated samples were used to modify glassy carbon (GC) electrode. The effect of applied acid treatment on the electrochemical behavior of GC electrodes modified with these materials was investigated. Furthermore, the effect of the introduction of nickel into acid treated samples was studied. The incorporation of nickel into acid treated bentonite was achieved by either ion exchange or impregnation/decomposition method. The obtained samples were characterized using the following methods: inductively coupled plasma (ICP), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy. The electrochemical behavior of these samples was tested by cyclic voltammetry in 0.1 mol dm-3 H2SO4 solution. The ICP, FTIR and ESR results exhibited a slight decrease of iron content in the acid treated samples. XRD and FTIR results confirmed that the conditions applied for the acid treatment were mild enough for the smectite structure to be preserved. The electrocatalytic test showed that the current response of Fe2+/Fe3+ oxidation/reduction process increased on the GC electrodes separately modified with each of the acid treated samples in comparison with current obtained on the GC electrode modified with untreated sample. These results indicated that applied acid treatment probably increased the accessibility of the electroactive iron within smectite. Cyclic voltammograms obtained for the GC electrodes modified with acid treated bentonite materials showed greater anodic charge (qa) than cathodic charge (qc). This difference might be due to iron detachment from smectite structure during the oxidation process. Further modification of the selected acid treated sample with nickel species resulted in decreased current response of the Fe2+/Fe3+ oxidation

  13. EFFECT OF ADDED WATER AND ACIDITY OF SIMULATED RAIN ON GROWTH OF FIELD-GROWN RADISH

    EPA Science Inventory

    Radish plants were grown in field plots and exposed to simulated rain at four levels of acidity: pH 5.6, pH 4.2, pH 3.5 and pH 2.8. Simulated rain solutions, containing background ions and acidified with a mixture of sulphuric and nitric acids, were applied intermittently between...

  14. DEMONSTRATION OF THE GLYCOLIC-FORMIC FLOWSHEET IN THE SRNL SHIELDED CELLS USING ACTUAL WASTE

    SciTech Connect

    Lambert, D.; Pareizs, J.; Click, D.

    2011-11-07

    Glycolic acid was effective at dissolving many metals, including iron, during processing with simulants. Criticality constraints take credit for the insolubility of iron during processing to prevent criticality of fissile materials. Testing with actual waste was needed to determine the extent of iron and fissile isotope dissolution during Chemical Process Cell (CPC) processing. The Alternate Reductant Project was initiated by the Savannah River Remediation (SRR) Company to explore options for the replacement of the nitric-formic flowsheet used for the CPC at the Defense Waste Processing Facility (DWPF). The goals of the Alternate Reductant Project are to reduce CPC cycle time, increase mass throughput of the facility, and reduce operational hazards. In order to achieve these goals, several different reductants were considered during initial evaluations conducted by Savannah River National Laboratory (SRNL). After review of the reductants by SRR, SRNL, and Energy Solutions (ES) Vitreous State Laboratory (VSL), two flowsheets were further developed in parallel. The two flowsheet options included a nitric-formic-glycolic flowsheet, and a nitric-formic-sugar flowsheet. As of July 2011, SRNL and ES/VSL have completed the initial flowsheet development work for the nitric-formic-glycolic flowsheet and nitric-formic-sugar flowsheet, respectively. On July 12th and July 13th, SRR conducted a Systems Engineering Evaluation (SEE) to down select the alternate reductant flowsheet. The SEE team selected the Formic-Glycolic Flowsheet for further development. Two risks were identified in SEE for expedited research. The first risk is related to iron and plutonium solubility during the CPC process with respect to criticality. Currently, DWPF credits iron as a poison for the fissile components of the sludge. Due to the high iron solubility observed during the flowsheet demonstrations with simulants, it was necessary to determine if the plutonium in the radioactive sludge slurry

  15. Optimization of [11C]HCN production and no-carrier-added [1-11C]amino acid synthesis.

    PubMed

    Iwata, R; Ido, T; Takahashi, T; Nakanishi, H; Iida, S

    1987-01-01

    The optimal conditions for the catalytic production of [11C]HCN from [11C]CO2 were investigated. [11C]CO2 was reduced to [11C]CH4 with H2 on Ni and then converted to [11C]HCN by reaction with NH3 on Pt in a radiochemical yield of more than 95% under the optimized conditions of an NH3 concentration of 5 vol%, a Pt furnace temperature of 920 degrees C, and a reaction gas flow rate of over 200 mL/min. Absorbers were used to remove O2 and H2O from the reaction gas. The synthesis of no-carrier-added [1-11C]amino acids from [11C]HCN via [11C]aminonitriles was successfully carried out. This method is suitable for automation of [1-11C]amino acid production. PMID:3032866

  16. RETRACTED: Crystal growth and spectroscopic characterization of Aloevera amino acid added lithium sulfate monohydrate: A non-linear optical crystal

    NASA Astrophysics Data System (ADS)

    Manimekalai, R.; Antony Joseph, A.; Ramachandra Raja, C.

    2014-03-01

    This article has been retracted: please see Elsevier Policy on Article Withdrawal. This article has been retracted at the request of authors. According to the author we have reported Aloevera Amino Acid added Lithium sulphate monohydrate [AALSMH] crystal is a new nonlinear optical crystal. From the recorded high performance liquid chromatography spectrum, by matching the retention times with the known compounds, the amino acids present in our extract are identified as homocystine, isoleucine, serine, leucine and tyrosine. From the thin layer chromatography and colorimetric estimation techniques, presence of isoleucine was identified and it was also confirmed by NMR spectrum. From the above studies, we came to conclude that AALSMH is new nonlinear optical crystal. After further investigation, lattice parameter values of AALSMH are coinciding with lithium sulphate. Therefore we have decided to withdraw our paper. Sorry for the inconvenience and time spent.

  17. Promoted degradation of perfluorooctanic acid by persulfate when adding activated carbon.

    PubMed

    Lee, Yu-Chi; Lo, Shang-Lien; Kuo, Jeff; Huang, Chin-Pao

    2013-10-15

    Treatment of persistent perfluorooctanoic acid (PFOA) in water using persulfate (PS) oxidation typically requires an elevated temperature or UV irradiation, which is energy-consuming. Under relatively low temperatures of 25-45°C, activated carbon (AC) activated PS oxidation of PFOA was evaluated for its potential of practical applications. With presence of AC in PS oxidation, PFOA removal efficiency at 25°C reached 682% with a high defluorination efficiency of 549% after 12h and few intermediates of short-chain perfluorinated carboxylic acids (PFCAs) were found. The removal and defluorination rates with the combined AC/PS system were approximately 12 and 19 times higher than those of the PS-only system, respectively. Activated carbon not only removes PFOA through adsorption, but also activates PS to form sulfate radicals that accelerate the decomposition and mineralization of PFOA. The activation energy for PS oxidation of PFOA was reduced from 668 to 261kJ/mol by the catalytic effect of AC, which implies a lower reaction temperature and a shorter reaction time would suffice. A 2-cycle schematic reaction mechanism was used to describe PS oxidation of PFOA with the generation of various intermediates and end-products. PMID:23978721

  18. Docosahexaenoic acid triglyceride-based microemulsions with an added dendrimer - Structural considerations.

    PubMed

    Lidich, Nina; Francesca Ottaviani, M; Hoffman, Roy E; Aserin, Abraham; Garti, Nissim

    2016-12-01

    Omega fatty acids, mainly the triglyceride of docosahexaenoic acid (TG-DHA), are considered important nutraceuticals. These compounds are water-insoluble and their transport across membranes depends on their carriers. Dendrimers are known as drug carriers across cell membranes and also as permeation enhancers. The solubilization of TG-DHA and dendrimer into a microemulsion (ME) system serving as a carrier could be used for a targeted delivery in the future. The interactions between TG-DHA and second generation poly(propyleneimine) dendrimers (PPI-G2) and their effect on structural transitions of ME were explored along the water dilution line using electron paramagnetic resonance and pulsed-gradient spin-echo NMR along with other analytical techniques. The microviscosity, order parameter, and micropolarity of all studied systems decrease upon water dilution. Incorporation of TG-DHA reduces the microviscosity, order, and micropolarity, whereas PPI-G2 leads to an increase in these parameters. The effect of PPI-G2 is more pronounced at relative high contents (1 and 5wt%) where PPI-G2 interacts with the hydrophilic headgroups of the surfactants. In the macroscale, the effects of TG-DHA and PPI-G2 differ mostly in the bicontinuous region, where macroviscosity increases upon TG-DHA incorporation and decreases upon solubilization of 5wt% PPI-G2. From DSC measurements it was concluded that in the presence of TG-DHA the PPI-G2 is intercalated easily at the interface. PMID:27571688

  19. Hydrogen generation in SRAT with nitric acid and late washing flowsheets

    SciTech Connect

    Hsu, C.W.

    1992-10-26

    Recently, SRTC recommended two process changes: (1) a final wash of the tetraphenylborate precipitate feed slurry and (2) the use of nitric acid to neutralize the sludge in the SRAT. The first change produced an aqueous hydrolysis product (PHA) with higher formic acid/formate and copper concentration, and reduced the nitrate content in the PHA by an order of magnitude. The second change is to substitute part of formic acid added to the SRAT with nitric acid, and therefore may reduce the hydrogen generated in the SRAT as well as provide nitrate as an oxidant to balance the redox state of the melter feed. The purpose of this report is to determine the pertinent variables that could affect the hydrogen generation rate with these process changes.

  20. CHARACTERIZATION OF INDIVIDUAL CHEMICAL REACTIONS CONSUMING ACID DURING NUCLEAR WASTE PROCESSING AT THE SAVANNAH RIVER SITE - 136B

    SciTech Connect

    Koopman, D.; Pickenheim, B.; Lambert, D.; Newell, J.; Stone, M.

    2009-09-02

    Conversion of legacy radioactive high-level waste at the Savannah River Site into a stable glass waste form involves a chemical pretreatment process to prepare the waste for vitrification. Waste slurry is treated with nitric and formic acids to achieve certain goals. The total quantity of acid added to a batch of waste slurry is constrained by the catalytic activity of trace noble metal fission products in the waste that can convert formic acid into hydrogen gas at many hundreds of times the radiolytic hydrogen generation rate. A large block of experimental process simulations were performed to characterize the chemical reactions that consume acid prior to hydrogen generation. The analysis led to a new equation for predicting the quantity of acid required to process a given volume of waste slurry.

  1. Mechanical and Electrical Characteristics of Poly-Lactic Acid which Added Plasticizer

    NASA Astrophysics Data System (ADS)

    Shinyama, Katsuyoshi; Fujita, Shigetaka

    Poly-lactic acid (PLA), a biodegradable plastic, has excellent electrical insulation properties. Being a hard resin, however, PLA is difficult to apply to coated cable. In this study, we blended a plasticizer with PLA to soften it, and examined the effects of the plasticizer on the mechanical and electrical characteristics of PLA. The glass transition temperature (Tg) and the melting point (Tm) had a tendency to decrease with an increase in the amount of plasticizer. With an increase in the amount of plasticizer, the tensile strength had a tendency to decrease and the breaking elongation to increase. As described above, PLA became softer with an increase in the amount of plasticizer. At 25°C, dielectric breakdown strength (EB) was about 5 MV/cm, irrespective of the presence of the plasticizer; the plasticizer showed almost no effect on EB. At 80°C, however, EB had a tendency to increase with an increase in the amount of plasticizer.

  2. Comparison of microbial sulfuric acid production in sewage sludge from added sulfur and thiosulfate

    SciTech Connect

    Tyagi, R.D.; Blais, J.F.; Deschenes, L.

    1994-09-01

    Microbial leaching is one of the most attractive methods of removing toxic metals from sewage sludge. Sulfuric acid produced by indigenous microflora by the oxidation of elemental sulfur and sulfur compounds solubilizes toxic metals. The oxidation of sulfur compounds can be achieved by the direct oxidation to sulfates or by indirect oxidation, through the production and accumulation of soluble intermediate S{sub 2}O{sub 3}{sup 2}{sup -}, S{sub 3}O{sup 6}{sup 2}{sup -}, S{sub 4}O{sub 6}{sup 2}{sup -} compounds. The production of these intermediates may create a potential danger of acidification of the receiving waters or the agricultural soil where the leached sludge is ultimately destined, via slow oxidation of the intermediates with subsequent sulfuric acid production. The objective of this research was to investigate the formation of S{sub 2}O{sub 3}{sup 2}{sup -}, S{sub 3}O{sub 6}{sup 2}{sup -}, and S{sub 4}O{sub 6}{sup 2} during metal bioleaching using elemental sulfur and thiosulfate as energy substrates for growth of indigenous thiobacilli (sulfur-oxidizing microorganisms) in sludge. The results obtained showed that intermediates were not formed when elemental sulfur was used as a substrate, whereas trithionate and tetrathionate and tetrathionate accumulated in the sludges when thiosulfate was used as substrate. Moreover, the metabolism of thiosulfate was much slower than that of elemental sulfur in sludge medium. Therefore, the utilization of thiosulfate for the growth of indigenous thiobacilli in sewage sludge is a less attractive alternative for the metal bioleaching. 33 refs., 3 figs., 2 tabs.

  3. Value-added lipid production from brown seaweed biomass by two-stage fermentation using acetic acid bacterium and thraustochytrid.

    PubMed

    Arafiles, Kim Hazel V; Iwasaka, Hiroaki; Eramoto, Yuri; Okamura, Yoshiko; Tajima, Takahisa; Matsumura, Yukihiko; Nakashimada, Yutaka; Aki, Tsunehiro

    2014-11-01

    Thraustochytrid production of polyunsaturated fatty acids and xanthophylls have been generally sourced from crop-derived substrates, making the exploration of alternative feedstocks attractive since they promise increased sustainability and lower production costs. In this study, a distinct two-stage fermentation system was conceptualized for the first time, using the brown seaweed sugar mannitol as substrate for the intermediary biocatalyst Gluconobacter oxydans, an acetic acid bacterium, along with the marine thraustochytrid Aurantiochytrium sp. to produce the value-added lipids and xanthophylls. Jar fermenter culture resulted in seaweed mannitol conversion to fructose with an efficiency of 83 % by G. oxydans and, after bacteriostasis with sea salts, production of astaxanthin and docosahexaenoic acid by Aurantiochytrium sp. KH105. Astaxanthin productivity was high at 3.60 mg/L/day. This new system, therefore, widens possibilities of obtaining more varieties of industrially valuable products including foods, cosmetics, pharmaceuticals, and biofuel precursor lipids from seaweed fermentation upon the use of suitable thraustochytrid strains. PMID:25086614

  4. Valorization of biodiesel derived glycerol as a carbon source to obtain added-value metabolites: Focus on polyunsaturated fatty acids.

    PubMed

    Abad, Sergi; Turon, Xavier

    2012-01-01

    The amount of glycerol derived from the biodiesel industry is exponentially increasing. The valorization of glycerol has acquired attention and resources with an obvious economic and environmental interest. Glycerol has the potential to improve the profitability of biodiesel in a biorefinery scenario. Added-value metabolites obtained from glycerol-based fermentations are the target of multiple research studies, primarily chemicals and biopolymers. Pigments and polyunsaturated fatty acids are exceptional examples as they have market presence as nutraceuticals. Most of the studies reviewed have been based on microalgae cultures. Depending on the strain and the engineering aspects of such cultures the final yield suffers notable variations. This is an emerging field which shows great potential from the perspective of a byproduct usage and the increasing yields (value) obtained from the bioprocess. PMID:22261015

  5. Adding monounsaturated fatty acids to a dietary portfolio of cholesterol-lowering foods in hypercholesterolemia

    PubMed Central

    Jenkins, David J.A.; Chiavaroli, Laura; Wong, Julia M.W.; Kendall, Cyril; Lewis, Gary F.; Vidgen, Edward; Connelly, Philip W.; Leiter, Lawrence A.; Josse, Robert G.; Lamarche, Benoît

    2010-01-01

    Background Higher intake of monounsaturated fat may raise high-density lipoprotein (HDL) cholesterol without raising low-density lipoprotein (LDL) cholesterol. We tested whether increasing the monounsaturated fat content of a diet proven effective for lowering LDL cholesterol (dietary portfolio) also modified other risk factors for cardiovascular disease, specifically by increasing HDL cholesterol, lowering serum triglyceride and further reducing the ratio of total to HDL cholesterol. Methods Twenty-four patients with hyperlipidemia consumed a therapeutic diet very low in saturated fat for one month and were then randomly assigned to a dietary portfolio low or high in monounsaturated fatty acid for another month. We supplied participants’ food for the two-month period. Calorie intake was based on Harris–Benedict estimates for energy requirements. Results For patients who consumed the dietary portfolio high in monounsaturated fat, HDL cholesterol rose, whereas for those consuming the dietary portfolio low in monounsaturated fat, HDL cholesterol did not change. The 12.5% treatment difference was significant (0.12 mmol/L, 95% confidence interval [CI] 0.05 to 0.21, p = 0.003). The ratio of total to HDL cholesterol was reduced by 6.5% with the diet high in monounsaturated fat relative to the diet low in monounsaturated fat (−0.28, 95% CI −0.59 to −0.04, p = 0.025). Patients consuming the diet high in monounsaturated fat also had significantly higher concentrations of apolipoprotein AI, and their C-reactive protein was significantly lower. No treatment differences were seen for triglycerides, other lipids or body weight, and mean weight loss was similar for the diets high in monounsaturated fat (−0.8 kg) and low in monounsaturated fat (−1.2 kg). Interpretation Monounsaturated fat increased the effectiveness of a cholesterol-lowering dietary portfolio, despite statin-like reductions in LDL cholesterol. The potential benefits for cardiovascular risk were

  6. Added value of hepatobiliary phase gadoxetic acid-enhanced MRI for diagnosing hepatocellular carcinoma in high-risk patients

    PubMed Central

    Phongkitkarun, Sith; Limsamutpetch, Kuruwin; Tannaphai, Penampai; Jatchavala, Janjira

    2013-01-01

    AIM: To determine the added value of hepatobiliary phase (HBP) gadoxetic acid-enhanced magnetic resonance imaging (MRI) in evaluating hepatic nodules in high-risk patients. METHODS: The institutional review board approved this retrospective study and waived the requirement for informed consent. This study included 100 patients at high risk for hepatocellular carcinoma (HCC) and 105 hepatic nodules that were larger than 1 cm. A blind review of two MR image sets was performed in a random order: set 1, unenhanced (T1- and T2-weighted) and dynamic images; and set 2, unenhanced, dynamic 20-min and HBP images. The diagnostic accuracy, sensitivity, specificity, positive predictive value (PPV), and negative predictive value (NPV) were compared for the two image sets. Univariate and multivariate analyses were performed on the MR characteristics utilized to diagnose HCC. RESULTS: A total of 105 hepatic nodules were identified in 100 patients. Fifty-nine nodules were confirmed to be HCC. The diameter of the 59 HCCs ranged from 1 to 12 cm (mean: 1.9 cm). The remaining 46 nodules were benign (28 were of hepatocyte origin, nine were hepatic cysts, seven were hemangiomas, one was chronic inflammation, and one was focal fat infiltration). The diagnostic accuracy significantly increased with the addition of HBP images, from 88.7% in set 1 to 95.5% in set 2 (P = 0.002). In set 1 vs set 2, the sensitivity and NPV increased from 79.7% to 93.2% and from 78.9% to 91.8%, respectively, whereas the specificity and PPV were not significantly different. The hypointensity on the HBP images was the most sensitive (93.2%), and typical arterial enhancement followed by washout was the most specific (97.8%). The multivariate analysis revealed that typical arterial enhancement followed by washout, hyperintensity on T2-weighted images, and hypointensity on HBP images were statistically significant MRI findings that could diagnose HCC (P < 0.05). CONCLUSION: The addition of HBP gadoxetic acid

  7. Antioxidant activity of phenolic compounds added to a functional emulsion containing omega-3 fatty acids and plant sterol esters.

    PubMed

    Espinosa, Raquel Rainho; Inchingolo, Raffaella; Alencar, Severino Matias; Rodriguez-Estrada, Maria Teresa; Castro, Inar Alves

    2015-09-01

    The effect of eleven compounds extracted from red propolis on the oxidative stability of a functional emulsion was evaluated. Emulsions prepared with Echium oil as omega 3 (ω-3 FA) source, containing 1.63 g/100mL of α-linolenic acid (ALA), 0.73 g/100 mL of stearidonic acid (SDA) and 0.65 g/100mL of plant sterol esters (PSE) were prepared without or with phenolic compounds (vanillic acid, caffeic acid, trans-cinnamic acid, 2,4-dihydroxycinnamic acid, p-coumaric acid, quercetin, trans-ferulic acid, trans,trans-farnesol, rutin, gallic acid or sinapic acid). tert-Butylhydroquinone and a mixture containing ascorbic acid and FeSO4 were applied as negative and positive controls of the oxidation. Hydroperoxide, thiobarbituric acid reactive substances (TBARS), malondialdehyde and phytosterol oxidation products (POPs) were evaluated as oxidative markers. Based on hydroperoxide and TBARS analysis, sinapic acid and rutin (200 ppm) showed the same antioxidant activity than TBHQ, representing a potential alternative as natural antioxidant to be applied in a functional emulsion containing ω-3 FA and PSE. PMID:25842314

  8. Comparison of acid generation in EUV lithography films of poly(4-hydroxystyrene) (PHS) and noria adamantyl ester (Noria-AD(50)).

    PubMed

    Wu, Weiqiang; Nuzhdin, Kirill; Vyushkova, Mariya; Janik, Ireneusz; Bartels, David

    2012-05-31

    The mechanism for acid production in phenolic extreme ultraviolet (EUV) lithography films containing triphenylsulfonium triflate (Ph(3)S(+)TfO(-)) acid generator has been investigated by electron paramagnetic resonance (EPR) spectroscopy and by use of the acid indicator coumarin 6 (C6). Gamma radiolysis was substituted for the EUV radiation with the assumption that the chemistry generated by ionization of the matrix does not depend on the ionization source. Poly(4-hydroxystyrene) (PHS) was first investigated as a well-studied standard, after which the water-wheel-like cyclic oligomer derivative containing pendant adamantyl ester groups, noria-AD(50), was investigated. EPR measurements confirm that the dominant free radical product is a phenoxyl derivative (PHS-O(•) or noria-O(•)) that exhibits quite slow stretched exponential recombination kinetics at room temperature. Also observed at 77 K was the presence of a significant hydrogen atom product of radiolysis. The G value or yield of acid production in thin lithography films was measured with the C6 indicator on a fused silica substrate. It was found that a significant amount of acid is generated via energy transfer from the irradiated fused-silica substrate to the Ph(3)S(+)TfO(-) in the films. By varying the film thickness on the substrates, the substrate effect on the acid yield was quantitatively determined. After subtraction of the contribution from the substrates, the acid yield G value in the PHS film with 10 wt % Ph(3)S(+)TfO(-) and 5 wt % C6 was determined to be 2.5 ± 0.3 protons per 100 eV of radiation. The acid yield of noria-AD(50) films was found to be 3.2 ± 0.3 protons per 100 eV. PMID:22607084

  9. ION-EXCLUSION CHROMATOGRAPHIC DETERMINATION OF CARBOXYLIC ACIDS USED TO SUPPORT THE MICROBIALLY MEDIATED REDUCTIVE DECHLORINATION OF TETRACHLOROETHENE

    EPA Science Inventory

    An analytical method was developed for the determination of lactic acid, formic acid, acetic acid, propionic acid, and butyric acid in environmental microcosm samples using ion-exclusion chromatography. The chromatographic behavior of various eluents was studied to determine the ...

  10. Generation of Bioactive Oxylipins from Exogenously Added Arachidonic, Eicosapentaenoic and Docosahexaenoic Acid in Primary Human Brain Microvessel Endothelial Cells.

    PubMed

    Aukema, Harold M; Winter, Tanja; Ravandi, Amir; Dalvi, Siddhartha; Miller, Donald W; Hatch, Grant M

    2016-05-01

    The human blood-brain barrier (BBB) is the restrictive barrier between the brain parenchyma and the circulating blood and is formed in part by microvessel endothelial cells. The brain contains significant amounts of arachidonic acid (ARA), and docosahexaenoic acid (DHA), which potentially give rise to the generation of bioactive oxylipins. Oxylipins are oxygenated fatty acid metabolites that are involved in an assortment of biological functions regulating neurological health and disease. Since it is not known which oxylipins are generated by human brain microvessel endothelial cells (HBMECs), they were incubated for up to 30 min in the absence or presence of 0.1-mM ARA, eicosapentaenoic acid (EPA) or DHA bound to albumin (1:1 molar ratio), and the oxylipins generated were examined using high performance liquid chromatography-tandem mass spectrometry (HPLC/MS/MS). Of 135 oxylipins screened in the media, 63 were present at >0.1 ng/mL at baseline, and 95 were present after incubation with fatty acid. Oxylipins were rapidly generated and reached maximum levels by 2-5 min. While ARA, EPA and DHA each stimulated the production of oxylipins derived from these fatty acids themselves, ARA also stimulated the production of oxylipins from endogenous 18- and 20-carbon fatty acids, including α-linolenic acid. Oxylipins generated by the lipoxygenase pathway predominated both in resting and stimulated states. Oxylipins formed via the cytochrome P450 pathway were formed primarily from DHA and EPA, but not ARA. These data indicate that HBMECs are capable of generating a plethora of bioactive lipids that have the potential to modulate BBB endothelial cell function. PMID:26439837

  11. Production of a value-added hydroxy fatty acid, 7,10-dihydroxy-8(E)-octadecenoic acid from high oleic safflower oil by Pseudomonas aeruginosa PR3

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Hydroxy fatty acids (HFA), originally found in small amount mainly from plant systems, are good examples of the structurally modified lipids, rendering special properties such as higher viscosity and reactivity compared to normal fatty acids. Based on these properties, HFAs possess high industrial ...

  12. Bacterial and Protozoal Communities and Fatty Acid Profile in the Rumen of Sheep Fed a Diet Containing Added Tannins ▿

    PubMed Central

    Vasta, Valentina; Yáñez-Ruiz, David R.; Mele, Marcello; Serra, Andrea; Luciano, Giuseppe; Lanza, Massimiliano; Biondi, Luisa; Priolo, Alessandro

    2010-01-01

    This study evaluated the effects of tannins on ruminal biohydrogenation (BH) due to shifts in the ruminal microbial environment in sheep. Thirteen lambs (45 days of age) were assigned to two dietary treatments: seven lambs were fed a barley-based concentrate (control group) while the other six lambs received the same concentrate with supplemental quebracho tannins (9.57% of dry matter). At 122 days of age, the lambs were slaughtered, and the ruminal contents were subjected to fatty acid analysis and sampled to quantify populations of Butyrivibrio fibrisolvens, which converts C18:2 c9-c12 (linoleic acid [LA]) to C18:2 c9-t11 (rumenic acid [RA]) and then RA to C18:1 t11 (vaccenic acid [VA]); we also sampled for Butyrivibrio proteoclasticus, which converts VA to C18:0 (stearic acid [SA]). Tannins increased (P < 0.005) VA in the rumen compared to the tannin-free diet. The concentration of SA was not affected by tannins. The SA/VA ratio was lower (P < 0.005) for the tannin-fed lambs than for the controls, suggesting that the last step of the BH process was inhibited by tannins. The B. proteoclasticus population was lower (−30.6%; P < 0.1), and B. fibrisolvens and protozoan populations were higher (+107% and +56.1%, respectively; P < 0.05) in the rumen of lambs fed the tannin-supplemented diet than in controls. These results suggest that quebracho tannins altered BH by changing ruminal microbial populations. PMID:20173064

  13. Bacterial and protozoal communities and fatty acid profile in the rumen of sheep fed a diet containing added tannins.

    PubMed

    Vasta, Valentina; Yáñez-Ruiz, David R; Mele, Marcello; Serra, Andrea; Luciano, Giuseppe; Lanza, Massimiliano; Biondi, Luisa; Priolo, Alessandro

    2010-04-01

    This study evaluated the effects of tannins on ruminal biohydrogenation (BH) due to shifts in the ruminal microbial environment in sheep. Thirteen lambs (45 days of age) were assigned to two dietary treatments: seven lambs were fed a barley-based concentrate (control group) while the other six lambs received the same concentrate with supplemental quebracho tannins (9.57% of dry matter). At 122 days of age, the lambs were slaughtered, and the ruminal contents were subjected to fatty acid analysis and sampled to quantify populations of Butyrivibrio fibrisolvens, which converts C(18:2) c9-c12 (linoleic acid [LA]) to C(18:2) c9-t11 (rumenic acid [RA]) and then RA to C(18:1) t11 (vaccenic acid [VA]); we also sampled for Butyrivibrio proteoclasticus, which converts VA to C(18:0) (stearic acid [SA]). Tannins increased (P < 0.005) VA in the rumen compared to the tannin-free diet. The concentration of SA was not affected by tannins. The SA/VA ratio was lower (P < 0.005) for the tannin-fed lambs than for the controls, suggesting that the last step of the BH process was inhibited by tannins. The B. proteoclasticus population was lower (-30.6%; P < 0.1), and B. fibrisolvens and protozoan populations were higher (+107% and +56.1%, respectively; P < 0.05) in the rumen of lambs fed the tannin-supplemented diet than in controls. These results suggest that quebracho tannins altered BH by changing ruminal microbial populations. PMID:20173064

  14. Increased brain uptake of targeted nanoparticles by adding an acid-cleavable linkage between transferrin and the nanoparticle core.

    PubMed

    Clark, Andrew J; Davis, Mark E

    2015-10-01

    Most therapeutic agents are excluded from entering the central nervous system by the blood-brain barrier (BBB). Receptor mediated transcytosis (RMT) is a common mechanism used by proteins, including transferrin (Tf), to traverse the BBB. Here, we prepared Tf-containing, 80-nm gold nanoparticles with an acid-cleavable linkage between the Tf and the nanoparticle core to facilitate nanoparticle RMT across the BBB. These nanoparticles are designed to bind to Tf receptors (TfRs) with high avidity on the blood side of the BBB, but separate from their multidentate Tf-TfR interactions upon acidification during the transcytosis process to allow release of the nanoparticle into the brain. These targeted nanoparticles show increased ability to cross an in vitro model of the BBB and, most important, enter the brain parenchyma of mice in greater amounts in vivo after systemic administration compared with similar high-avidity nanoparticles containing noncleavable Tf. In addition, we investigated this design with nanoparticles containing high-affinity antibodies (Abs) to TfR. With the Abs, the addition of the acid-cleavable linkage provided no improvement to in vivo brain uptake for Ab-containing nanoparticles, and overall brain uptake was decreased for all Ab-containing nanoparticles compared with Tf-containing ones. These results are consistent with recent reports of high-affinity anti-TfR Abs trafficking to the lysosome within BBB endothelium. In contrast, high-avidity, Tf-containing nanoparticles with the acid-cleavable linkage avoid major endothelium retention by shedding surface Tf during their transcytosis. PMID:26392563

  15. Thermal and mechanical properties of polylactic acid (PLA) and bagasse carboxymethyl cellulose (CMCB) composite by adding isosorbide diesters

    NASA Astrophysics Data System (ADS)

    Kamthai, Suthaphat; Magaraphan, Rathanawan

    2015-05-01

    An isosorbide diesters is one of isororbide types used as a plasticizer. The influence of this plasticizer on thermal and mechanical properties of polylactic acid and bagasse carboxymethyl cellulose (PLA/CMCB) composites was studied. PLA was blended with CMCB at 1%wt using various contents of isosorbide diesters (5, 10, 15 and 20%wt of PLA). The differential scanning calorimetric (DSC) and thermogravimetric (TGA) analyses indicated that the increment of isosorbide diesters concentration resulted in decreasing glass transition, melting and decomposition temperatures, as well as the reduction of storage modulus of PLA/CMCB composites. Moreover, the elongation of PLA/CMCB composites was significantly improved with increasing plasticizer content.

  16. Development and quality of a Brazilian semi-hard goat cheese (coalho) with added probiotic lactic acid bacteria.

    PubMed

    Garcia, Estefânia Fernandes; de Oliveira, Maria Elieidy Gomes; Queiroga, Rita de Cássia Ramos Do Egypto; Machado, Tamires Alcântara Dourado; de Souza, Evandro Leite

    2012-12-01

    The effects of the addition of different strains of lactic acid bacteria on different quality parameters of a Brazilian goat semi-hard cheese (coalho) were assessed during 7 days of storage (10°C) as follows: Control, Lactobacillus lactis subsp. lactis and L. lactis subsp. cremoris (standard); C2, L. acidophilus; C3, L. paracasei; C4, Bifidobacterium lactis; and C5, L. acidophilus, L. paracasei and B. lactis. There were no differences for the proteolysis index and depth of proteolysis among the assessed cheeses. The cheeses presented increase in hardness, gumminess and chewiness during the storage. Regarding the ability to melt, all evaluated cheeses showed a reduction in diameter. Cheeses presented high luminosity with predominance of the yellow component; and number of lactic bacteria greater than 10⁶-10⁷ cfu/g during the 7 days of storage. C5 had better sensory scores in the acceptance test, purchase intention and preference ranking test. Coalho goat cheese could be a potential carrier of probiotic lactic acid bacteria. PMID:22574688

  17. Voluntary feed intake, acid-base balance and partitioning of urinary nitrogen in lambs fed corn silage with added sodium bicarbonate or sodium sesquicarbonate.

    PubMed

    Phillip, L E; Hidalgo, V

    1989-08-01

    An experiment with growing lambs was designed to test the hypothesis that alterations in blood acid-base status would influence intake of corn silage. Six wethers (29 kg) were fed a diet of corn silage (36% DM, 8% CP) supplemented with 1.25% urea and .2% sulfur. At feeding time, sodium bicarbonate (NaHCO3) and sodium sesquicarbonate (NaSC) were added to the silage at levels of 0, 2% or 4% of diet DM. The treatments were arranged as a 2 x 3 factorial, and the study was conducted as a 6 x 4 incomplete latin square with four 17-d periods. Voluntary intake of OM was not different (P greater than .05) between NaHCO3 (1,008 g/d) and NaSC (1,041 g/d). There was no significant interaction between type of buffer (NaHCO3 or NaSC) and level of buffer on any of the variables measured. The progressive increase in buffer load did not alter feed intake (P greater than .05), although there was a quadratic response (P less than .05) in urine pH and a linear increase (P less than .01) in blood HCO3- 2 h after feeding. There was no evidence that lambs fed corn silage experienced metabolic acid stress. Urinary excretion of ammonia and urea were indicative of changes, although not pronounced, in ammoniuria and ureapoiesis in response to bicarbonate loading. This study implies that corn silage imposes no "acid stress" on lambs and, consequently, that there is no nutritional benefit in adding buffers to corn silage for sheep. PMID:2551870

  18. Value Added?

    ERIC Educational Resources Information Center

    UCLA IDEA, 2012

    2012-01-01

    Value added measures (VAM) uses changes in student test scores to determine how much "value" an individual teacher has "added" to student growth during the school year. Some policymakers, school districts, and educational advocates have applauded VAM as a straightforward measure of teacher effectiveness: the better a teacher, the better students…

  19. Effects of the storage time on the folic acid added to ready-to-eat meat products manufactured by irradiation

    NASA Astrophysics Data System (ADS)

    Galán, I.; García, M. L.; Selgas, M. D.

    2013-04-01

    Three different meat products enriched with folic acid (FA) (2.4 mg/100 g) were manufactured: hamburgers, cooked and dry fermented sausages. They were prepared as ready-to-eat (RTE) products using E-beam radiation (2 and 3 kGy) to ensure their safety. The stability of FA and sensory properties of the irradiated meat products were studied during three months of storage under freezing conditions for hamburgers and refrigeration conditions for cooked and dry fermented sausages. FA content was stable in non-irradiated and irradiated hamburgers and cooked sausages over the storage period, whereas it decreased 20% in non-irradiated dry fermented sausages and 12-8% in irradiated samples at 2 and 3 kGy, respectively. Nevertheless, the final amount remained sufficient to provide the recommended daily intake. Panelists rated the sensory properties of the hamburger as satisfactory even after irradiation and 90 days of storage. The overall acceptability of RTE cooked and dry fermented sausages improved slightly with storage (P>0.05).

  20. Use of weak acids to determine the bulk diffusion limitation of H+ ion conductance through the gramicidin channel.

    PubMed Central

    Decker, E R; Levitt, D G

    1988-01-01

    The addition of 2 M formic acid at pH 3.75 increased the single channel H+ ion conductance of gramicidin channels 12-fold at 200 mV. Other weak acids (acetic, lactic, oxalic) produce a similar, but smaller increase. Formic acid (and other weak acids) also blocks the K+ conductance at pH 3.75, but not at pH 6.0 when the anion form predominates. This increased H+ conductance and K+ block can be explained by formic acid (HF) binding to the mouth of the gramicidin channel (Km = 1 M) and providing a source of H+ ions. A kinetic model is derived, based on the equilibrium binding of formic acid to the channel mouth, that quantitatively predicts the conductance for different mixtures of H+, K+, and formic acid. The binding of the neutral formic acid to the mouth of the gramicidin channel is directly supported by the observation that a neutral molecule with a similar structure, formamide (and malonamide and acrylamide), blocks the K+ conductance at pH 6.0. The H+ conductance in the presence of formic acid provides a lower bound for the intrinsic conductance of the gramicidin channel when there is no diffusion limitation at the channel mouth. The 12-fold increase in conductance produced by formic acid suggests that greater than 90% of the total resistance to H+ results from diffusion limitation in the bulk solution. PMID:2449253

  1. Inactivation of Salmonella enterica and Listeria monocytogenes in cantaloupe puree by high hydrostatic pressure with/without added ascorbic acid.

    PubMed

    Mukhopadhyay, Sudarsan; Sokorai, Kimberly; Ukuku, Dike; Fan, Xuetong; Juneja, Vijay; Sites, Joseph; Cassidy, Jennifer

    2016-10-17

    The objective of this research was to evaluate and develop a method for inactivation of Salmonella enterica and Listeria monocytogenes in cantaloupe puree (CP) by high hydrostatic pressure (HHP). Cantaloupe being the most netted varieties of melons presents a greater risk of pathogen transmission. Freshly prepared CP with or without 0.1% ascorbic acid (AA) was inoculated with a bacterial cocktail composed of a three serotype mixture of S. enterica (S. Poona, S. Newport H1275 and S. Stanley H0558) and a mixture of three strains of L. monocytogenes (Scott A, 43256 and 51742) to a population of ca. 10(8)CFU/g. Double sealed and double bagged inoculated CP (ca. 5g) were pressure treated at 300, 400 and 500MPa at 8°C and 15°C for 5min. Data indicated increased inactivation of both Salmonella and Listeria spp. with higher pressure. Log reduction for CP at 300MPa, 8°C for 5min was 2.4±0.2 and 1.6±0.5logCFU/g for Salmonella and Listeria, respectively. Survivability of the pathogens was significantly compromised at 400MPa and 8°C, inactivating 4.5±0.3logCFU/g of Salmonella and 3.0±0.4logCFU/g of Listeria spp. Complete inactivation of the pathogens in the puree (log reduction >6.7logCFU/g), with or without AA, was achieved when the pressure was further increased to 500MPa, except that for Listeria containing no AA at 8°C. Listeria presented higher resistance to pressure treatment compared to Salmonella spp. Initial temperatures (8 and 15°C) had no significant influence on Salmonella log reductions. Log reduction of pathogens increased but not significantly with increase of temperature. AA did not show any significant antimicrobial activity. Viable counts were about 0.2-0.4logCFU/g less in presence of 0.1% AA. These data validate that HHP can be used as an effective method for decontamination of cantaloupe puree. PMID:27441819

  2. Effects of large doses of arachidonic acid added to docosahexaenoic acid on social impairment in individuals with autism spectrum disorders: a double-blind, placebo-controlled, randomized trial.

    PubMed

    Yui, Kunio; Koshiba, Mamiko; Nakamura, Shun; Kobayashi, Yuji

    2012-04-01

    Autism spectrum disorders are a neurodevelopmental disorders with reduced cortical functional connectivity relating to social cognition. Polyunsaturated fatty acids arachidonic acid (ARA) and docosahexaenoic acid (DHA) may have key role in brain network maturation. In particularly, ARA is important in signal transduction related to neuronal maturation. Supplementation with larger ARA doses added to DHA may therefore mitigate social impairment. In a 16-week, double-blind, randomized, placebo-controlled trial, we evaluated the efficacy of supplementation with large doses of ARA added to DHA (n = 7) or placebo (n = 6) in 13 participants (mean age, 14.6 [SD, 5.9] years). To examine underlying mechanisms underlying the effect of our supplementation regimen, we examined plasma levels of antioxidants transferrin and superoxide dismutase, which are useful markers of signal transduction. The outcome measures were the Social Responsiveness Scale and the Aberrant Behavior Checklist-Community. Repeated-measures analysis of variance revealed that our supplementation regimen significantly improved Aberrant Behavior Checklist-Community-measured social withdrawal and Social Responsiveness Scale-measured communication. Treatment effect sizes were more favorable for the treatment group compared with the placebo group (communication: treatment groups, 0.87 vs, placebo, 0.44; social withdrawal: treatment groups, 0.88, vs placebo, 0.54). There was a significant difference in the change in plasma transferrin levels and a trend toward a significant difference in the change in plasma superoxide dismutase levels between the 2 groups. This preliminary study suggests that supplementation with larger ARA doses added to DHA improves impaired social interaction in individuals with autism spectrum disorder by up-regulating signal transduction. PMID:22370992

  3. Adding Value.

    ERIC Educational Resources Information Center

    Orsini, Larry L.; Hudack, Lawrence R.; Zekan, Donald L.

    1999-01-01

    The value-added statement (VAS), relatively unknown in the United States, is used in financial reports by many European companies. Saint Bonaventure University (New York) has adapted a VAS to make it appropriate for not-for-profit universities by identifying stakeholder groups (students, faculty, administrators/support personnel, creditors, the…

  4. [Comparison of demineralization of different organic acid to enamel].

    PubMed

    Liu, L; Yue, S; Jiang, H; Lu, T

    1998-05-01

    The rates of demineralization of 5 organic acids (mathanoic acid, formic acid, propionic acid, Lactic acid, acetic acid, mixed acid) to the bovine enamel were tested and analysed with the self-made calcium ionselective microelectrodes(Ca(2+)-ISME) basing on a neutral carriers of ETH1001. The results showed; 1. The difference between the rates of demineralization of formic acid and lactic acid, formic acid and propionic acid, formic acid and acetic acid, acetic acid and mixed acid, acetic acid and lactic acid, propionic acid and mixed acid, propionic acid and lactic acid, lactic acid and mixed acid were of great significance (P < 0.01); 2. The rates of demineralization of acetic and mixed acid decreased with time, due to saturation of the solution during demineralization; 3. Ca(2+)-ISME was of the advantages of simplicity, rapidity, sensitivity and accuracy. The results suggest that the cariogenic potential is related to different acid products of different cariogenic bacteria, and the degree of mineral saturation within solution affects the rate of demineralization. PMID:12214404

  5. [Therapeutic effects of larger doses of arachidonic acid added to DHA on social impairment and its relation to alterations of polyunsaturated fatty acids in individuals with autism spectrum disorders].

    PubMed

    Yui, Kunio; Koshiba, Mamiko; Nakamura, Shun; Onishi, Masako

    2011-06-01

    The polyunsaturated fatty acids (PUFAs), arachidonic acid (ARA) and docosahexaenoic acid (DHA) may play key roles in brain network maturation. ARA plays an important role in signal transduction related to neuronal maturation. This study aims to evaluate the efficacy of supplementing with larger doses of ARA added to DHA in a double-blind, placebo-controlled 16-week trial. To confirm findings observed in the placebo-controlled trial, an additional 16-week open-label study was further conducted. To examine the relationship between the efficacy of the supplementation regimen and alterations in PUFAs levels, we examined plasma levels of PUFAs. We used the Social Responsiveness Scale (SRS) and the Aberrant Behavior Checklist-Community (ABC) to estimate psychotic symptoms. Repeated measures ANOVA revealed that this supplementation significantly improved SRS-measured communication as well as ABC-measured social withdrawal during the placebo-controlled trial. The treatment effect sizes were more favorable for the treatment group compared with the placebo group (communication: 0.87 vs. 0.44; social withdrawal: 0.88 vs. 0.54). At the end of the placebo-controlled trial, there was a significant difference in the change in plasma ARA levels from the baseline and a trend towards a significant difference in plasma ARA levels between the two groups. The open-label study was not powered to detect significant improvements in the outcome measures or significant differences in plasma ARA levels. The present clinical trials suggest that supplementation with larger ARA doses added to DHA improves social impairment in individuals with ASD via ARA-induced upregulation of neuronal functioning. PMID:21800702

  6. DIS in AdS

    NASA Astrophysics Data System (ADS)

    Albacete, Javier L.; Kovchegov, Yuri V.; Taliotis, Anastasios

    2009-03-01

    We calculate the total cross section for the scattering of a quark-anti-quark dipole on a large nucleus at high energy for a strongly coupled N = 4 super Yang-Mills theory using AdS/CFT correspondence. We model the nucleus by a metric of a shock wave in AdS5. We then calculate the expectation value of the Wilson loop (the dipole) by finding the extrema of the Nambu-Goto action for an open string attached to the quark and antiquark lines of the loop in the background of an AdS5 shock wave. We find two physically meaningful extremal string configurations. For both solutions we obtain the forward scattering amplitude N for the quark dipole-nucleus scattering. We study the onset of unitarity with increasing center-of-mass energy and transverse size of the dipole: we observe that for both solutions the saturation scale Qs is independent of energy/Bjorken-x and depends on the atomic number of the nucleus as Qs˜A1/3. Finally we observe that while one of the solutions we found corresponds to the pomeron intercept of αP = 2 found earlier in the literature, when extended to higher energy or larger dipole sizes it violates the black disk limit. The other solution we found respects the black disk limit and yields the pomeron intercept of αP = 1.5. We thus conjecture that the right pomeron intercept in gauge theories at strong coupling may be αP = 1.5.

  7. DIS in AdS

    SciTech Connect

    Albacete, Javier L.; Kovchegov, Yuri V.; Taliotis, Anastasios

    2009-03-23

    We calculate the total cross section for the scattering of a quark-anti-quark dipole on a large nucleus at high energy for a strongly coupled N = 4 super Yang-Mills theory using AdS/CFT correspondence. We model the nucleus by a metric of a shock wave in AdS{sub 5}. We then calculate the expectation value of the Wilson loop (the dipole) by finding the extrema of the Nambu-Goto action for an open string attached to the quark and antiquark lines of the loop in the background of an AdS{sub 5} shock wave. We find two physically meaningful extremal string configurations. For both solutions we obtain the forward scattering amplitude N for the quark dipole-nucleus scattering. We study the onset of unitarity with increasing center-of-mass energy and transverse size of the dipole: we observe that for both solutions the saturation scale Q{sub s} is independent of energy/Bjorken-x and depends on the atomic number of the nucleus as Q{sub s}{approx}A{sup 1/3}. Finally we observe that while one of the solutions we found corresponds to the pomeron intercept of {alpha}{sub P} = 2 found earlier in the literature, when extended to higher energy or larger dipole sizes it violates the black disk limit. The other solution we found respects the black disk limit and yields the pomeron intercept of {alpha}{sub P} = 1.5. We thus conjecture that the right pomeron intercept in gauge theories at strong coupling may be {alpha}{sub P} = 1.5.

  8. Mystery cloud of AD 536

    NASA Technical Reports Server (NTRS)

    Stothers, R. B.

    1984-01-01

    The possible cause of the densest and most persistent dry fog on record, which was observed in Europe and the Middle East during AD 536 and 537, is discussed. The fog's long duration toward the south and the high sulfuric acid signal detected in Greenland in ice cores dated around AD 540 support the theory that the fog was due to the explosion of the Rabaul volcano, the occurrence of which has been dated at about AD 540 by the radiocarbon method.

  9. [Inhibition of Low Molecular Organic Acids on the Activity of Acidithiobacillus Species and Its Effect on the Removal of Heavy Metals from Contaminated Soil].

    PubMed

    Song, Yong-wei; Wang, He-rul; Cao, Yan-xiao; Li, Fei; Cui, Chun-hong; Zhou, Li

    2016-05-15

    Application of organic fertilizer can reduce the solubility and bioavailability of heavy metals in contaminated soil, but in the flooded anaerobic environment, organic fertilizer will be decomposed to produce a large number of low molecular organic acids, which can inhibit the biological activity of Acidithiobacillus species. Batch cultures studies showed that the monocarboxylic organic acids including formic acid, acetic acid, propionic acid, and butyric acid exhibited a marked toxicity to Acidithiobacillus species, as indicated by that 90% of inhibitory rate for Fe2 and So oxidation in 72 h were achieved at extremely low concentrations of 41.2 mg · L⁻¹, 78.3 mg · L⁻¹, 43.2 mg · L⁻¹, 123.4 mg · L⁻¹ and 81.9 mg 230. 4 mg · L⁻¹, 170.1 mg · L⁻¹, 123.4 mg · L⁻¹ respectively. Of these organic acids, formic acid was the most toxic one as indicated by that Fe2 and So oxidation was almost entirely inhibited at a low concentration. In addition, it was found that Acidithiobacillus ferrooxidans was more sensitive to low molecular organic acids than Acidithiobacillus thiooxidans. What's more, there was little effect on biological acidification process of heavy metal contaminated soil when organic acids were added at initial stage (Oh), but it was completely inhibited when these acids were added after 12 h of conventional biological acidification, thus decreasing the efficiency of heavy metals dissolution from soil. PMID:27506054

  10. Bubbling AdS3

    NASA Astrophysics Data System (ADS)

    Martelli, Dario; Morales, Jose F.

    2005-02-01

    In the light of the recent Lin, Lunin, Maldacena (LLM) results, we investigate 1/2-BPS geometries in minimal (and next to minimal) supergravity in D = 6 dimensions. In the case of minimal supergravity, solutions are given by fibrations of a two-torus T2 specified by two harmonic functions. For a rectangular torus the two functions are related by a non-linear equation with rare solutions: AdS3 × S3, the pp-wave and the multi-center string. ``Bubbling'', i.e. superpositions of droplets, is accommodated by allowing the complex structure of the T2 to vary over the base. The analysis is repeated in the presence of a tensor multiplet and similar conclusions are reached, with generic solutions describing D1D5 (or their dual fundamental string-momentum) systems. In this framework, the profile of the dual fundamental string-momentum system is identified with the boundaries of the droplets in a two-dimensional plane.

  11. In vitro response of Staphylococcus aureus from cystic fibrosis patients to combinations of linoleic and oleic acids added to nutrient medium.

    PubMed Central

    Campbell, I M; Crozier, D N; Pawagi, A B; Buivids, I A

    1983-01-01

    The effect of supplementing nutrient substrate with various combinations of concentrations of oleic and linoleic acids on the growth of 11 strains of Staphylococcus aureus was assessed. Whereas increasing the concentration of linoleic acid by itself greatly diminished the growth of all 11 strains, concomitant increases in oleic acid greatly diminished the inhibitory effect of linoleic acid. With oleic acid in the nutrient substrate, most of the strains were induced to produce slime which surrounded the cells. Since the slime incorporated oleic but not linoleic acid, such slime production isolated the cells from direct contact with the growth inhibitor, linoleic acid. Images PMID:6619290

  12. Formation of Iron Complexes from Trifluoroacetic Acid Based Liquid Chromatography Mobile Phases as Interference Ions in LC-ESI-MS Analysis

    PubMed Central

    Shukla, Anil; Zhang, Rui; Orton, Daniel; Zhao, Rui; Clauss, Therese; Moore, Ronald; Smith, Richard

    2011-01-01

    Two unexpected singly charged ions at m/z 1103 and 944 have been observed in mass spectra obtained from electrospray ionization-mass spectrometric analysis of liquid chromatography effluents with mobile phases containing trifluoroacetic acid that severely interfered with sample analysis. Accurate mass measurement and tandem mass spectrometry studies revealed that these two ions are composed of three components; clusters of trifluoroacetic acid, clusters of mass 159 and iron. Formation of these ions is inhibited by removing trifluoroacetic acid from the mobile phases and using formic acid in its place, replacing the stainless steel union with a titanium union or by adding a small blank fused silica capillary column between the chromatography column and the electrospray tip via a stainless steel union without any adverse effects to chromatographic separation, peak broadening or peptide identifications. PMID:21504012

  13. Determination of Acid Herbicides Using Modified QuEChERS with Fast Switching ESI(+)/ESI(-) LC-MS/MS.

    PubMed

    Sack, Chris; Vonderbrink, John; Smoker, Michael; Smith, Robert E

    2015-11-01

    A method for the determination of 35 acid herbicides in food matrices was developed, validated, and implemented. It utilizes a modified QuEChERS extraction procedure coupled with quantitation by liquid chromatography tandem mass spectrometry (LC-MS/MS). The acid herbicides analyzed are all organic carboxylic acids, including the older chlorophenoxy acid herbicides such as 2,4-dichlorophenoxyacetic acid (2,4-D), dicamba, 4-chlorophenoxyacetic acid (4-CPA), quinclorac, and many of the newer imidazolinone herbicides such as imazethapyr and imazaquin. In the procedure, 10 mL of water is added to 5 g of sample and then extracted with 1% formic acid in acetonitrile for 1 min. The acetonitrile phase is salted out of the extract by adding sodium chloride and magnesium sulfate, followed by centrifugation. The acetonitrile is diluted 1:1 with water to enable quantitation by LC-MS/MS using fast switching between positive and negative electrospray ionization modes. The average recoveries for all the compounds except aminocyclopyrachlor were 95% with a precision of 8%. The method detection limits for all residues were less than 10 ng/g, and the correlation coefficients for the calibration curves was greater than 0.99 for all but two compounds tested. The method was used successfully for the quantitation of acid herbicides in the FDA's total diet study. The procedure proved to be accurate, precise, linear, sensitive, and rugged. PMID:26473587

  14. [Inhibition of growth of microscopic fungi with organic acids].

    PubMed

    Conková, E; Para, L; Kocisová, A

    1993-01-01

    Fungicidal effects of five selected organic acids (lactic, acetic, formic, oxalic, and propionic) in concentrations 3, 5, 10, 20 and 50 ml/l on nine selected species of moulds were tested. Lactic and oxalic acids did not prove the satisfactory fungicidal activity in any of the chosen concentrations. The antifungal effect of the other three acids, manifested by the growth inhibition of the tested moulds is shown in Tab. I and it can be expressed by sequence: propionic acid, formic acid, and acetic acid. These acids also had effects only in concentrations 20 ml/l and 50 ml/l. Propionic acid in concentration 20 ml/l inhibited the growth of five moulds (Penicillium glabrum, Aspergillus niger, Fusarium moniliforme, Aspergillus fumigatus, Cladosporium sphaerospermum). In testing of concentration 50 ml/l, the lower fungicidal ability was ascertained only in growth suppression of Aspergillus flavus. The fungicidal activity of formic acid was registered in concentration 20 ml/l in two cases and in concentration 50 ml/l in six cases. Acetic acid inhibited the growth in concentration 50 ml/l only in two cases. Tab. II shows the percentual evaluation of propionic acid and formic acid with regard to their inhibition abilities. The fungicidal efficiency of propionic acid resulting from the experiment is 88.9%. PMID:8122343

  15. GLYCOLIC ACID PHYSICAL PROPERTIES, IMPURITIES, AND RADIATION EFFECTS ASSESSMENT

    SciTech Connect

    Pickenheim, B.; Bibler, N.

    2010-06-08

    The DWPF is pursuing alternative reductants/flowsheets to increase attainment to meet closure commitment dates. In fiscal year 2009, SRNL evaluated several options and recommended the further assessment of the nitric/formic/glycolic acid flowsheet. SRNL is currently performing testing with this flowsheet to support the DWPF down-select of alternate reductants. As part of the evaluation, SRNL was requested to determine the physical properties of formic and glycolic acid blends. Blends of formic acid in glycolic acid were prepared and their physical properties tested. Increasing amounts of glycolic acid led to increases in blend density, viscosity and surface tension as compared to the 90 wt% formic acid that is currently used at DWPF. These increases are small, however, and are not expected to present any difficulties in terms of processing. The effect of sulfur impurities in technical grade glycolic acid was studied for its impact on DWPF glass quality. While the glycolic acid specification allows for more sulfate than the current formic acid specification, the ultimate impact is expected to be on the order of 0.03 wt% sulfur in glass. Note that lower sulfur content glycolic acid could likely be procured at some increased cost if deemed necessary. A paper study on the effects of radiation on glycolic acid was performed. The analysis indicates that substitution of glycolic acid for formic acid would not increase the radiolytic production rate of H{sub 2} and cause an adverse effect in the SRAT or SME process. It has been cited that glycolic acid solutions that are depleted of O{sub 2} when subjected to large radiation doses produced considerable quantities of a non-diffusive polymeric material. Considering a constant air purge is maintained in the SRAT and the solution is continuously mixed, oxygen depletion seems unlikely, however, if this polymer is formed in the SRAT solution, the rheology of the solution may be affected and pumping of the solution may be

  16. Development of a pH sensor based on a nanostructured filter adding pH-sensitive fluorescent dye for detecting acetic acid in photovoltaic modules

    NASA Astrophysics Data System (ADS)

    Asaka, Takashi; Itayama, Tomohiro; Nagasaki, Hideaki; Iwami, Kentaro; Yamamoto, Chizuko; Hara, Yukiko; Masuda, Atsushi; Umeda, Norihiro

    2015-08-01

    Acetic acid formed via the hydrolysis of ethylene vinyl acetate (EVA) as an encapsulant in photovoltaic (PV) modules causes a decrease in the conversion efficiency of such modules by grid corrosion. Here, a nondestructive and simple optical method for evaluating the condition of PV modules is proposed. This method uses a dual-wavelength pH-sensitive fluorescent dye to detect acetic acid in PV modules using a change in pH. The change in pH induced by the formation of acetic acid is detected by the change in the ratio of the fluorescent intensities of two peaks of the dye. A pH-sensitive fluorescent dye showed sensitivity for small amounts of acetic acid such as that produced from EVA. Furthermore, a membrane filter dyed with a pH-sensitive fluorescent dye was confirmed to detect acetic acid in aged EVA after a damp-heat test (85 °C, 85%) for 5000 h in PV modules.

  17. Polarised black holes in AdS

    NASA Astrophysics Data System (ADS)

    Costa, Miguel S.; Greenspan, Lauren; Oliveira, Miguel; Penedones, João; Santos, Jorge E.

    2016-06-01

    We consider solutions in Einstein-Maxwell theory with a negative cosmological constant that asymptote to global AdS 4 with conformal boundary {S}2× {{{R}}}t. At the sphere at infinity we turn on a space-dependent electrostatic potential, which does not destroy the asymptotic AdS behaviour. For simplicity we focus on the case of a dipolar electrostatic potential. We find two new geometries: (i) an AdS soliton that includes the full backreaction of the electric field on the AdS geometry; (ii) a polarised neutral black hole that is deformed by the electric field, accumulating opposite charges in each hemisphere. For both geometries we study boundary data such as the charge density and the stress tensor. For the black hole we also study the horizon charge density and area, and further verify a Smarr formula. Then we consider this system at finite temperature and compute the Gibbs free energy for both AdS soliton and black hole phases. The corresponding phase diagram generalizes the Hawking-Page phase transition. The AdS soliton dominates the low temperature phase and the black hole the high temperature phase, with a critical temperature that decreases as the external electric field increases. Finally, we consider the simple case of a free charged scalar field on {S}2× {{{R}}}t with conformal coupling. For a field in the SU(N ) adjoint representation we compare the phase diagram with the above gravitational system.

  18. Nitric acid requirement for treating sludge

    SciTech Connect

    Hsu, C.W.

    1992-09-04

    The hydroxylamine nitrate (HAN) precipitate hydrolysis process produces sufficient oxidant (nitrate) such that the resulting blend of formic acid treated sludge and the aqueous product from hydrolysis (PHA) produces a melter feed of acceptable redox (i.e. Fe+2/Total Fe <0.33). With implementation of Late Washing (to reduce the nitrite content of the tetraphenyborate slurry produced during In-Tank Precipitation to 0.01M or less), HAN is no longer required during hydrolysis. As a result, the nitrate content of the melter feed will be reduced greater than an order-of-magnitude and the resulting melter feed produced will be too reducing. If formic acid treatment of the sludge is retained, it will be necessary to trim the melter feed with an oxidant to attain a proper redox. Rather than trimming the melter feed with an oxidant subsequent to the SRAT cycle in which formic acid is used to acidify the sludge, the Savannah River Technology Center (SRTC) has recommended this be accomplished by conversion to nitric acid addition to the Sludge Receipt and Adjustment Tank (SRAT) in place of formic acid (1). This memorandum specifies the stoichiometric bases for determining the nitric acid requirement for the SRAT.

  19. GLYCOLIC-NITRIC ACID FLOWSHEET DEMONSTRATION OF THE DWPF CHEMICAL PROCESSING CELL WITH MATRIX SIMULANTS AND SUPERNATE

    SciTech Connect

    Lambert, D.; Stone, M.; Newell, J.; Best, D.

    2012-05-07

    Savannah River Remediation (SRR) is evaluating changes to its current DWPF flowsheet to improve processing cycle times. This will enable the facility to support higher canister production while maximizing waste loading. Higher throughput is needed in the CPC since the installation of the bubblers into the melter has increased melt rate. Due to the significant maintenance required for the DWPF gas chromatographs (GC) and the potential for production of flammable quantities of hydrogen, reducing or eliminating the amount of formic acid used in the CPC is being developed. Earlier work at Savannah River National Laboratory has shown that replacing formic acid with an 80:20 molar blend of glycolic and formic acids has the potential to remove mercury in the SRAT without any significant catalytic hydrogen generation. This report summarizes the research completed to determine the feasibility of processing without formic acid. In earlier development of the glycolic-formic acid flowsheet, one run (GF8) was completed without formic acid. It is of particular interest that mercury was successfully removed in GF8, no formic acid at 125% stoichiometry. Glycolic acid did not show the ability to reduce mercury to elemental mercury in initial screening studies, which is why previous testing focused on using the formic/glycolic blend. The objective of the testing detailed in this document is to determine the viability of the nitric-glycolic acid flowsheet in processing sludge over a wide compositional range as requested by DWPF. This work was performed under the guidance of Task Technical and Quality Assurance Plan (TT and QAP). The details regarding the simulant preparation and analysis have been documented previously.

  20. GLYCOLIC-NITRIC ACID FLOWSHEET DEMONSTRATION OF THE DWPF CHEMICAL PROCESS CELL WITH SLUDGE AND SUPERNATE SIMULANTS

    SciTech Connect

    Lambert, D.; Stone, M.; Newell, J.; Best, D.; Zamecnik, J.

    2012-08-28

    Savannah River Remediation (SRR) is evaluating changes to its current Defense Waste Processing Facility (DWPF) flowsheet to improve processing cycle times. This will enable the facility to support higher canister production while maximizing waste loading. Higher throughput is needed in the Chemical Process Cell (CPC) since the installation of the bubblers into the melter has increased melt rate. Due to the significant maintenance required for the DWPF gas chromatographs (GC) and the potential for production of flammable quantities of hydrogen, reducing or eliminating the amount of formic acid used in the CPC is being developed. Earlier work at Savannah River National Laboratory has shown that replacing formic acid with an 80:20 molar blend of glycolic and formic acids has the potential to remove mercury in the SRAT without any significant catalytic hydrogen generation. This report summarizes the research completed to determine the feasibility of processing without formic acid. In earlier development of the glycolic-formic acid flowsheet, one run (GF8) was completed without formic acid. It is of particular interest that mercury was successfully removed in GF8, no formic acid at 125% stoichiometry. Glycolic acid did not show the ability to reduce mercury to elemental mercury in initial screening studies, which is why previous testing focused on using the formic/glycolic blend. The objective of the testing detailed in this document is to determine the viability of the nitric-glycolic acid flowsheet in processing sludge over a wide compositional range as requested by DWPF. This work was performed under the guidance of Task Technical and Quality Assurance Plan (TT&QAP). The details regarding the simulant preparation and analysis have been documented previously.

  1. Δ(9) desaturase protein expression and fatty acid composition of longissimus dorsi muscle in lambs fed green herbage or concentrate with or without added tannins.

    PubMed

    Vasta, Valentina; Priolo, Alessandro; Scerra, Manuel; Hallett, Katharine G; Wood, Jeffrey D; Doran, Olena

    2009-07-01

    The aims of this study were to investigate the effect of feeding system and of supplementation of tannins (8.93% DM) on the relationship between intramuscular fat content, fatty acid composition and Δ(9)desaturase (Δ(9)d) protein expression in longissimus dorsi muscle of lamb. Twenty-eight Comisana lambs (age 45days) were fed either vetch (Vicia sativa) or concentrate. The herbage diet was (i) lower in saturated fatty acids (especially in C16:0), C18:1 n-9 and in C18:2 n-6; (ii) higher in C16:1 and C18:3 n-3 when compared to concentrate. Within each feeding system the lambs were divided into two sub-groups, one of which received the diet without tannins supplementation, and the other was fed the diets supplemented with the tannins from Quebracho (Schinopsis lorentzii). The animals were slaughtered at age 105days. The concentrate feeding system increased (p<0.01) the total intramuscular fat content and the amount of SFA, MUFA and n-6 PUFA and decreased the level of n-3 PUFA (p=0.05) when compared to the vetch-fed animals but did not affect Δ(9) desaturase protein expression. There was no correlation between Δ(9)d protein expression and total intramuscular fatty acids, CLA and MUFA level. It was suggested that in ruminants, in contrast to monogastric animals, Δ(9)d expression does not play the key role in intramuscular fatty acids formation. Tannins supplementation resulted in higher (p<0.05) muscle levels of transC18:1 and C18:2 n-6. It has also increased Δ(9)d expression in the case of herbage-based diet but not in the case of concentrate-based diet. The mechanism of tannins action on the enzyme expression needs to be elucidated. PMID:20416712

  2. Effects of linseed and quercetin added to the diet of fattening lambs on the fatty acid profile and lipid antioxidant status of meat samples.

    PubMed

    Andrés, S; Morán, L; Aldai, N; Tejido, M L; Prieto, N; Bodas, R; Giráldez, F J

    2014-06-01

    Thirty-two Merino lambs fed barley straw and a concentrate formulated either with palm oil (CTRL group) or with linseed (+LS group), both alone or supplemented with quercetin (+QCT group or +LS+QCT group) were used to assess the effects of these dietary supplements on meat quality attributes. After being slaughtered, the longissimus thoracis muscles were used to study the fatty acid (FA) profile in detail, whilst longissimus lumborum slices were stored under refrigerated conditions to determine the lipid stability. Linseed increased the content of highly unsaturated n-3 long-chain fatty acid (20:5n-3; 22:5n-3; 22:6n-3). Interestingly, a significant increment of rumenic acid content (9c,11t-18:2) was observed when this seed was administered together with dietary quercetin. Moreover, the feeding of quercetin resulted in a reduction in the proportion of saturated FA and a decrease in lipid peroxidation of meat when the lambs were fed linseed. In conclusion, from both a nutritional and a commercial (shelf-life) point of view, it may be useful to include a source of quercetin when lambs are fed linseed diets. PMID:24583323

  3. Treatment of coal and formic acid mixtures with water at supercritical parameters

    SciTech Connect

    M.R. Predtechenskii; M.V. Pukhovoi; A.N. Smal; A.O. Uuemaa

    2007-08-15

    The treatment of coals of various degrees of metamorphism in supercritical water (SCW) over the temperature region 380-800{sup o}C was studied. The possibility of obtaining strong agglomerates from the powders of long-flame and oxidized fat noncoking coals by treatment in SCW was demonstrated. The strength of agglomerates was commensurable with the strength of lump coal.

  4. Effect of adding amino acids residues in N- and C-terminus of Vip3Aa16 (L121I) toxin.

    PubMed

    Sellami, Sameh; Cherif, Marwa; Jamoussi, Kaïs

    2016-06-01

    To study the importance of N- and C-terminus of Bacillus thuringiensis Vip3Aa16 (L121I) toxin (88 kDa), a number of mutants were generated. The addition of two (2R: RS) or eleven (11R: RSRPGHHHHHH) amino acid residues at the Vip3Aa16 (L121I) C-terminus allowed to an unappropriated folding illustrated by the abundant presence of the 62 kDa proteolytic form. The produced Vip3Aa16 (L121I) full length form was less detected when increasing the number of amino acids residues in the C-terminus. Bioassays demonstrated that the growth of the lepidopteran Ephestia kuehniella was slightly affected by Vip3Aa16 (L121I)-2R and not affected by Vip3Aa16 (L121I)-11R. Additionally, the fusion at the Vip3Aa16 (L121I) N-terminus of 39 amino acids harboring the E. coli OmpA leader peptide and the His-tag sequence allowed to the increase of protease sensitivity of Vip3Aa16 (L121I) full length form, as only the 62 kDa proteolysis form was detected. Remarkably, this fused protein produced in Escherichia coli (E. coli) was biologically inactive toward Ephestia kuehniella larvae. Thus, the N-terminus of the protein is required to the accomplishment of the insecticidal activity of Vip3 proteins. This report serves as guideline for the study of Vip3Aa16 (L121I) protein stability and activity. PMID:26876111

  5. Ice core profiles of saturated fatty acids (C12:0-C30:0) and oleic acid (C18:1) from southern Alaska since 1734 AD: A link to climate change in the Northern Hemisphere

    NASA Astrophysics Data System (ADS)

    Pokhrel, Ambarish; Kawamura, Kimitaka; Seki, Osamu; Matoba, Sumio; Shiraiwa, Takayuki

    2015-01-01

    An ice core drilled at Aurora Peak in southeast Alaska was analyzed for homologous series of straight chain fatty acids (C12:0-C30:0) including unsaturated fatty acid (oleic acid) using gas chromatography (GC/FID) and GC/mass spectrometry (GC/MS). Molecular distributions of fatty acids are characterized by even carbon number predominance with a peak at palmitic acid (C16:0, av. 20.3 ± SD. 29.8 ng/g-ice) followed by oleic acid (C18:1, 19.6 ± 38.6 ng/g-ice) and myristic acid (C14:0, 15.3 ± 21.9 ng/g-ice). The historical trends of short-chain fatty acids, together with correlation analysis with inorganic ions and organic tracers suggest that short-chain fatty acids (except for C12:0 and C15:0) were mainly derived from sea surface micro layers through bubble bursting mechanism and transported over the glacier through the atmosphere. This atmospheric transport process is suggested to be linked with Kamchatka ice core δD record from Northeast Asia and Greenland Temperature Anomaly (GTA). In contrast, long-chain fatty acids (C20:0-C30:0) are originated from terrestrial higher plants, soil organic matter and dusts, which are also linked with GTA. Hence, this study suggests that Alaskan fatty acids are strongly influenced by Pacific Decadal Oscillation/North Pacific Gyre Oscillation and/or extra tropical North Pacific surface climate and Arctic oscillation. We also found that decadal scale variability of C18:1/C18:0 ratios in the Aurora Peak ice core correlate with the Kamchatka ice core δD, which reflects climate oscillations in the North Pacific. This study suggests that photochemical aging of organic aerosols could be controlled by climate periodicity.

  6. Effects of an oral dose of l-glutamic acid on circulating neurotransmitters: Possible roles of the C1(Ad) and the A5(NA) pontomedullary nuclei

    PubMed Central

    Lechin, Fuad; van der Dijs, Bertha; Pardey-Maldonado, Betty; Rivera, Jairo E; Lechin, Marcel E; Baez, Scarlet

    2010-01-01

    Objective Investigation of the effects of an oral administration of a small dose of l-glutamic acid on the two peripheral sympathetic branches (neural and adrenal) of the autonomic nervous system. Research design and methods Circulating neurotransmitters and cardiovascular parameters were assessed in 28 healthy volunteers before and after the administration of 500 mg of l-glutamic acid or placebo. Results The drug triggered a significant and sustained enhancement of the noradrenaline and dopamine circulating levels which were paralleled and positively correlated with the diastolic blood pressure increases. Conversely, both platelet and plasma serotonin showed significant falls throughout the test. Significant positive correlations were registered between noradrenaline, dopamine, and noradrenaline/dopamine ratio versus diastolic blood pressure but not versus systolic blood pressure or heart rate. Conclusion The above results allowed us to postulate that the drug provoked a significant enhancement of peripheral neural sympathetic activity and the reduction of adrenal sympathetic and parasympathetic drives. Both sympathetic branches are positively correlated with the A5 noradrenergic and the C1 adrenergic pontomedullary nuclei, which interchange inhibitory axons that act at post-synaptic α2 inhibitory autoreceptors. In addition, we discussed the mechanisms able to explain why the drug acted preferentially at the A5 noradrenergic rather than the C1 adrenergic nuclei.

  7. Smeared antibranes polarise in AdS

    NASA Astrophysics Data System (ADS)

    Gautason, Fridrik Freyr; Truijen, Brecht; Van Riet, Thomas

    2015-07-01

    In the recent literature it has been questioned whether the local backreaction of antibranes in flux throats can induce a perturbative brane-flux decay. Most evidence for this can be gathered for D6 branes and D p branes smeared over 6 - p compact directions, in line with the absence of finite temperature solutions for these cases. The solutions in the literature have flat worldvolume geometries and non-compact transversal spaces. In this paper we consider what happens when the worldvolume is AdS and the transversal space is compact. We show that in these circumstances brane polarisation smoothens out the flux singularity, which is an indication that brane-flux decay is prevented. This is consistent with the fact that the cosmological constant would be less negative after brane-flux decay. Our results extend recent results on AdS7 solutions from D6 branes to AdS p+1 solutions from D p branes. We show that supersymmetry of the AdS solutions depend on p non-trivially.

  8. AdS orbifolds and Penrose limits

    SciTech Connect

    Alishahiha, Mohsen; Sheikh-Jabbari, Mohammad M.; Tatar, Radu

    2002-12-09

    In this paper we study the Penrose limit of AdS{sub 5} orbifolds. The orbifold can be either in the pure spatial directions or space and time directions. For the AdS{sub 5}/{Lambda} x S{sup 5} spatial orbifold we observe that after the Penrose limit we obtain the same result as the Penrose limit of AdS{sub 5} x S{sup 5}/{Lambda}. We identify the corresponding BMN operators in terms of operators of the gauge theory on R x S{sup 3}/{Lambda}. The semi-classical description of rotating strings in these backgrounds have also been studied. For the spatial AdS orbifold we show that in the quadratic order the obtained action for the fluctuations is the same as that in S{sup 5} orbifold, however, the higher loop correction can distinguish between two cases.

  9. Redox behavior of Ce(IV)/Ce(III) in the presence of nitrilotriacetic acid: A surrogate study for An(I\\T)/AD(III) redox behavior

    SciTech Connect

    Suzuki, Y.; Francis, A.; Nankawa, T.; Ohnuki, T.

    2010-07-01

    Using cyclic voltammetry, we investigated the redox behavior of Ce(IV)/Ce(III), which is a surrogate for An(IV)/An(III) (An=actinides), in a solution of nitrilotriacetic acid (NTA) at 25 C. The cyclic voltammogram of Ce in a 0.1 M NTA solution at pH 6 showed a reversible one-electron redox reaction for Ce(IV)/Ce(III) at 0.51 V vs. Ag/AgCl. This redox potential was much lower than that obtained in 1 M nitric acid, indicating that Ce(IV) was preferentially stabilized by complexation with NTA. The redox potential in the NTA solution was independent of the Ce concentration from 2 to 20 mM, NTA concentration from 5 to 200 mM and pH between 3 and 7. These results indicated that no polymerization and no additional coordination of NTA and OH{sup -} to the Ce(III)-NTA complex took place during the redox reaction. As the speciation calculation of Ce(III) in the NTA solution showed that the predominant species was Ce{sup III}(nta){sub 2}{sup 3-} (H{sub 3}nta = NTA), the redox reaction of the Ce-NTA complex was expressed by the following: Ce{sup IV}(nta){sub 2}{sup 2-} +e{sup -} Ce{sup III}(nta){sub 2}{sup 3-}. The logarithm of the stability constant of Ce{sup IV}(nta){sub 2}{sup 2-} was calculated to be 38.6 {+-} 0.8 for I = 0 from the redox potential shift of Ce(IV)/Ce(III) in the NTA solution. The value was in good accordance with the stability constant of the Np{sup IV}(nta){sub 2}{sup 2-} complex, demonstrating that the aqueous coordination chemistry of Ce(IV) with NTA is quite similar to that of An(IV). These results strongly suggest that a negative shift of the Pu(IV)/Pu(III) redox potential in the NTA solution should make Pu(IV) more stable than Pu(III) even in a reducing environment.

  10. On the dissolution kinetics of humic acid particles. Effect of monocarboxylic acids.

    PubMed

    Brigante, Maximiliano; Zanini, Graciela; Avena, Marcelo

    2008-05-01

    The dissolution kinetics of humic acid particles has been studied in batch experiments, and the effects of monocarboxylic (formic, acetic, and propionic) acids are reported. The dissolution rate of the particles is significantly affected by the presence of monocarboxylic acids in the pH range 4-10. At pH 7, for example, propionic acid increases 30 times this dissolution rate. The capacity of increasing the dissolution rate is in the order formic acidacidacid, and this dissolving capacity of carboxylics seems to be directly related to their affinity for HA molecules located at the surface of the solid particles. The results indicate that carboxylics and related compounds may affect markedly the mobility and transport of humic substances in the environment. PMID:18328533

  11. Added value of next generation gene panel analysis for patients with elevated methylmalonic acid and no clinical diagnosis following functional studies of vitamin B12 metabolism.

    PubMed

    Pupavac, Mihaela; Tian, Xia; Chu, Jordan; Wang, Guoli; Feng, Yanming; Chen, Stella; Fenter, Remington; Zhang, Victor W; Wang, Jing; Watkins, David; Wong, Lee-Jun; Rosenblatt, David S

    2016-03-01

    Next generation sequencing (NGS) based gene panel testing is increasingly available as a molecular diagnostic approach for inborn errors of metabolism. Over the past 40 years patients have been referred to the Vitamin B12 Clinical Research Laboratory at McGill University for diagnosis of inborn errors of cobalamin metabolism by functional studies in cultured fibroblasts. DNA samples from patients in which no diagnosis was made by these studies were tested by a NGS gene panel to determine whether any molecular diagnoses could be made. 131 DNA samples from patients with elevated methylmalonic acid and no diagnosis following functional studies of cobalamin metabolism were analyzed using the 24 gene extended cobalamin metabolism NGS based panel developed by Baylor Miraca Genetics Laboratories. Gene panel testing identified two or more variants in a single gene in 16/131 patients. Eight patients had pathogenic findings, one had a finding of uncertain significance, and seven had benign findings. Of the patients with pathogenic findings, five had mutations in ACSF3, two in SUCLG1 and one in TCN2. Thus, the NGS gene panel allowed for the presumptive diagnosis of 8 additional patients for which a diagnosis was not made by the functional assays. PMID:26827111

  12. Simple and Rapid Determination of Ferulic Acid Levels in Food and Cosmetic Samples Using Paper-Based Platforms

    PubMed Central

    Tee-ngam, Prinjaporn; Nunant, Namthip; Rattanarat, Poomrat; Siangproh, Weena; Chailapakul, Orawon

    2013-01-01

    Ferulic acid is an important phenolic antioxidant found in or added to diet supplements, beverages, and cosmetic creams. Two designs of paper-based platforms for the fast, simple and inexpensive evaluation of ferulic acid contents in food and pharmaceutical cosmetics were evaluated. The first, a paper-based electrochemical device, was developed for ferulic acid detection in uncomplicated matrix samples and was created by the photolithographic method. The second, a paper-based colorimetric device was preceded by thin layer chromatography (TLC) for the separation and detection of ferulic acid in complex samples using a silica plate stationary phase and an 85:15:1 (v/v/v) chloroform: methanol: formic acid mobile phase. After separation, ferulic acid containing section of the TLC plate was attached onto the patterned paper containing the colorimetric reagent and eluted with ethanol. The resulting color change was photographed and quantitatively converted to intensity. Under the optimal conditions, the limit of detection of ferulic acid was found to be 1 ppm and 7 ppm (S/N = 3) for first and second designs, respectively, with good agreement with the standard HPLC-UV detection method. Therefore, these methods can be used for the simple, rapid, inexpensive and sensitive quantification of ferulic acid in a variety of samples. PMID:24077320

  13. Embryo development and sex ratio of in vitro-produced porcine embryos are affected by the energy substrate and hyaluronic acid added to the culture medium.

    PubMed

    Torner, Eva; Bussalleu, Eva; Briz, M Dolors; Yeste, Marc; Bonet, Sergi

    2014-01-01

    In the present study, the effects of replacing glucose with pyruvate-lactate and supplementing these in vitro culture (IVC) media with hyaluronic acid (HA) on porcine embryo development and sex ratio were examined. The in vitro-produced (IVP) porcine embryos were cultured in NCSU-23 medium with 0.0, 0.5 or 1.0mgmL(-1) HA, and with either 5.55mM glucose (IVC-Glu) or pyruvate (0.17mM)-lactate (2.73mM) from 0 to 48h post insemination (h.p.i.) and then with glucose from 48 to 168h.p.i. (IVC-PL). Those embryos cultured with IVC-PL had significantly higher blastocyst rates (23.7±1.5%) than those cultured with IVC-Glu (14.27±2.75%). At 1.0mgmL(-1), HA tended to skew the sex ratio of blastocysts towards males in those embryos cultured in IVC-PL, and led to a significant decrease in the blastocyst rate compared with embryos cultured in the presence of 0.5 and 0.0mgmL(-1) HA and IVC-Glu (4.28±0.28% vs 11.01±1.42% and 10.14±2.77%, respectively) and IVC-PL (14.37±1.35% vs 20.96±2.85% and 22.99±1.39%, respectively). In contrast, there were no significant differences in the total cell number per blastocyst or in apoptosis rates. In conclusion, pyruvate and lactate were the preferred energy substrates in the early stages of IVP porcine embryos. Moreover, 1.0mgmL(-1) HA significantly decreased the percentage of blastocyst rates in both the IVC-Glu and IVC-PL groups, but only by a preferential loss of female embryos for those cultured in IVC-PL. PMID:23657201

  14. Ruthenium volatility from the vitrification of melter feeds prepared using the Nitric Acid Flowsheet

    SciTech Connect

    Hutson, N.D.

    1992-10-22

    The present DWPF flowsheet calls for the chemical treatment of waste sludge with 90 wt% formic acid prior to the addition of the Precipitate Hydrolysis Aqueous (PHA) product. An alternative processing methodology, denoted the ``Nitric Acid Flowsheet``, has been proposed. In the application of this flowsheet, nitric acid would be used to neutralize sludge base components (hydroxides and carbonates) prior to the addition of late wash PHA. The late wash PHA will contain sufficient quantities of formic acid to adequately complete necessary reduction-oxidation (REDOX) reactions.

  15. An evaluation of mercury removal in the IDMS using the nitric acid flowsheet

    SciTech Connect

    Hutson, N.D.

    1992-10-22

    The present DWPF flowsheet calls for the chemical treatment of waste sludge with 90 wt % formic acid prior to the addition of the Precipitate Hydrolysis Aqueous (PHA) product. An alternative processing methodology, denoted the ``Nitric Acid Flowsheet``, has been proposed. in the application of this flowsheet, nitric acid would be used to neutralize sludge base components (hydroxides and carbonates) prior to the addition of late wash PHA. The late wash PHA will contain sufficient quantities of formic acid to adequately complete necessary reduction-oxidation (REDOX) reactions.

  16. Ruthenium volatility from the vitrification of melter feeds prepared using the Nitric Acid Flowsheet

    SciTech Connect

    Hutson, N.D.

    1992-10-22

    The present DWPF flowsheet calls for the chemical treatment of waste sludge with 90 wt% formic acid prior to the addition of the Precipitate Hydrolysis Aqueous (PHA) product. An alternative processing methodology, denoted the Nitric Acid Flowsheet'', has been proposed. In the application of this flowsheet, nitric acid would be used to neutralize sludge base components (hydroxides and carbonates) prior to the addition of late wash PHA. The late wash PHA will contain sufficient quantities of formic acid to adequately complete necessary reduction-oxidation (REDOX) reactions.

  17. An evaluation of mercury removal in the IDMS using the nitric acid flowsheet

    SciTech Connect

    Hutson, N.D.

    1992-10-22

    The present DWPF flowsheet calls for the chemical treatment of waste sludge with 90 wt % formic acid prior to the addition of the Precipitate Hydrolysis Aqueous (PHA) product. An alternative processing methodology, denoted the Nitric Acid Flowsheet'', has been proposed. in the application of this flowsheet, nitric acid would be used to neutralize sludge base components (hydroxides and carbonates) prior to the addition of late wash PHA. The late wash PHA will contain sufficient quantities of formic acid to adequately complete necessary reduction-oxidation (REDOX) reactions.

  18. The AdS particle [rapid communication

    NASA Astrophysics Data System (ADS)

    Ghosh, Subir

    2005-09-01

    In this Letter we have considered a relativistic Nambu-Goto model for a particle in AdS metric. With appropriate gauge choice to fix the reparameterization invariance, we recover the previously discussed [S. Ghosh, P. Pal, Phys. Lett. B 618 (2005) 243, arxiv:hep-th/0502192] "exotic oscillator". The Snyder algebra and subsequently the κ-Minkowski spacetime are also derived. Lastly we comment on the impossibility of constructing a non-commutative spacetime in the context of open string where only a curved target space is introduced.

  19. Probing crunching AdS cosmologies

    NASA Astrophysics Data System (ADS)

    Kumar, S. Prem; Vaganov, Vladislav

    2016-02-01

    Holographic gravity duals of deformations of CFTs formulated on de Sitter spacetime contain FRW geometries behind a horizon, with cosmological big crunch singularities. Using a specific analytically tractable solution within a particular single scalar truncation of {N}=8 supergravity on AdS4, we first probe such crunching cosmologies with spacelike radial geodesics that compute spatially antipodal correlators of large dimension boundary operators. At late times, the geodesics lie on the FRW slice of maximal expansion behind the horizon. The late time two-point functions factorise, and when transformed to the Einstein static universe, they exhibit a temporal non-analyticity determined by the maximal value of the scale factor ã max. Radial geodesics connecting antipodal points necessarily have de Sitter energy Ɛ ≲ ã max, while geodesics with Ɛ > ã max terminate at the crunch, the two categories of geodesics being separated by the maximal expansion slice. The spacelike crunch singularity is curved "outward" in the Penrose diagram for the deformed AdS backgrounds, and thus geodesic limits of the antipodal correlators do not directly probe the crunch. Beyond the geodesic limit, we point out that the scalar wave equation, analytically continued into the FRW patch, has a potential which is singular at the crunch along with complex WKB turning points in the vicinity of the FRW crunch. We then argue that the frequency space Green's function has a branch point determined by ã max which corresponds to the lowest quasinormal frequency.

  20. Low-Molecular Weight Carboxylic Acids in Gas Phase in a Developing Megacity

    NASA Astrophysics Data System (ADS)

    Khwaja, H. A.; Saied, S.; Hussain, M. M.; Siddique, A.; Butts, C.; Kamran, S. S.; Khan, M. K.

    2013-12-01

    Carboxylic acids are amongst the plethora of pollutants that are currently ubiquitous in the environment. Molecular distributions of carboxylic acids have been studied in the atmosphere of the developing mega city Karachi, Pakistan. As a region the city is experiencing industrial and population growth at an unparallel rate. Karachi served as a great focal point to observe the effects of industrial development on a growing city and how it contributes to the progression of environmental pollution. Results indicate that acetic and formic acids are important components of the Karachi atmosphere. The most abundant acids, by a substantial margin, were acetic acid and formic acid, with concentrations of 0.70 - 14.2 ppb and 0.82 - 11.0 ppb, respectively. On the average acetic acid levels exceeded those of formic acid. Concentrations of propionic acid, pyruvic acid, and glyoxalic acid ranged 0.03 - 1.41, 0.01 - 0.28, and 0.02 - 0.14 ppb, respectively. The gaseous acids showed diurnal cycles, with higher mixing ratios during nighttime. Compared with other metropolitans in the world, the level of acetic and formic acid concentration of Karachi is much higher. The ratio of formic to acetic acid was used to distinguish primary sources from secondary sources. A mean ratio of 0.85 was found. A positive correlation (r = 0.65 - 0.94) was observed between the acid concentrations suggesting that they have similar sources. Carboxylic acid concentrations appear to arise both from direct emissions and from atmospheric oxidation of hydrocarbons.

  1. Quantification of Bile Acids in Traditional Animal Medicines and Their Preparations Using Ultra High-Performance Liquid Chromatography-Mass Spectrometry in the Multiple Reaction Monitoring Mode.

    PubMed

    Yerigui; Wu, Xiu-Hong; Wang, Xi-Jun; Ma, Chao-Mei

    2016-01-01

    An ultra-high-performance liquid chromatograph-triple quadrupole mass spectrometry has been established and validated for the simultaneous quantification of 15 bile acids in four traditional animal medicines and their preparations. The separations of bile acids were performed on an Agilent ZORBAX Eclipse XDB-C18 column (50 × 2.1 mm; 1.8 μm) with methanol-0.1% formic acid as the mobile phase. Glycyrrhetinic acid was added as internal standard owing to its similar physiochemical properties with the bile acids. Using this condition, detected in the multiple reaction monitoring mode, the 15 bile acids, including three groups of isomers, were well quantified individually. Method validation showed that the linear regression relationship (r(2), 0.9993 - 0.9999), precisions (intra-day RSD, 0.96 - 4.31%; inter-day, 1.73 - 4.43%), and recovery (95.3 - 120.9%) were all satisfactory. The analysis results showed that bear bile and bezoar (Niu Huang) as well as their formulations contained large amounts of most of the 15 bile acids. In addition, this research revealed for the first time the presences of bile acids in animal waste medication used in traditional medicine from two clinics, Hei-Bing-Pian (discharges of wild boar) and Trogopterus Dung. The established method could be used for the quantification of other bile- or animal waste-based crude drugs and their formulated products. PMID:27169647

  2. AdS3: the NHEK generation

    NASA Astrophysics Data System (ADS)

    Bena, Iosif; Heurtier, Lucien; Puhm, Andrea

    2016-05-01

    It was argued in [1] that the five-dimensional near-horizon extremal Kerr (NHEK) geometry can be embedded in String Theory as the infrared region of an infinite family of non-supersymmetric geometries that have D1, D5, momentum and KK monopole charges. We show that there exists a method to embed these geometries into asymptotically- {AdS}_3× {S}^3/{{Z}}_N solutions, and hence to obtain infinite families of flows whose infrared is NHEK. This indicates that the CFT dual to the NHEK geometry is the IR fixed point of a Renormalization Group flow from a known local UV CFT and opens the door to its explicit construction.

  3. Shadows, currents, and AdS fields

    SciTech Connect

    Metsaev, R. R.

    2008-11-15

    Conformal totally symmetric arbitrary spin currents and shadow fields in flat space-time of dimension greater than or equal to four are studied. A gauge invariant formulation for such currents and shadow fields is developed. Gauge symmetries are realized by involving the Stueckelberg fields. A realization of global conformal boost symmetries is obtained. Gauge invariant differential constraints for currents and shadow fields are obtained. AdS/CFT correspondence for currents and shadow fields and the respective normalizable and non-normalizable solutions of massless totally symmetric arbitrary spin AdS fields are studied. The bulk fields are considered in a modified de Donder gauge that leads to decoupled equations of motion. We demonstrate that leftover on shell gauge symmetries of bulk fields correspond to gauge symmetries of boundary currents and shadow fields, while the modified de Donder gauge conditions for bulk fields correspond to differential constraints for boundary conformal currents and shadow fields. Breaking conformal symmetries, we find interrelations between the gauge invariant formulation of the currents and shadow fields, and the gauge invariant formulation of massive fields.

  4. Effects of fish oil and starch added to a diet containing sunflower-seed oil on dairy goat performance, milk fatty acid composition and in vivo delta9-desaturation of [13C]vaccenic acid.

    PubMed

    Bernard, Laurence; Mouriot, Julien; Rouel, Jacques; Glasser, Frédéric; Capitan, Pierre; Pujos-Guillot, Estelle; Chardigny, Jean-Michel; Chilliard, Yves

    2010-08-01

    The potential benefits on human health have prompted an interest in developing nutritional strategies for specifically increasing rumenic acid (RA) in ruminant milk. The aims of the present study were to (i) compare two dietary treatments with lipid supplements on milk yield and composition, (ii) measure the in vivo delta9-desaturation of vaccenic acid (VA) to RA using 13C-labelled VA and (iii) determine the effect of the dietary treatments on this variable. Treatments were 90 g sunflower-seed oil (SO) per d or 60 g sunflower-seed oil and 30 g fish oil per d plus additional starch (SFO), in a grassland hay-based diet given to eight Alpine goats in a 2 x 2 cross-over design with 21 d experimental periods. Milk yield and composition were similar between treatments. Goats fed SFO had higher milk 6 : 0-16 : 0 concentration, lower milk sigmaC18 concentrations and showed no effect on milk VA and RA, compared with SO. At the end of the experiment, intravenous injection of 1.5 g [13C]VA followed by measurements of milk lipid 13C enrichment showed that in vivo 31.7 and 31.6 % of VA was delta9-desaturated into milk RA in the caprine with the SO and SFO treatments, respectively. The expression of genes encoding for delta9-desaturase (or stearoyl-CoA desaturase; SCD1, SCD5) in mammary tissues and four milk delta9-desaturation ratios were similar between treatments. In conclusion, the present study provides the first estimates of in vivo endogenous synthesis of RA (63-73 % of milk RA) from VA in goats, and shows no difference between the two lipid supplements compared. PMID:20307350

  5. GLYCOLIC ACID PHYSICAL PROPERTIES, IMPURITIES, AND RADIATION EFFECTS ASSESSMENT

    SciTech Connect

    Lambert, D.; Pickenheim, B.; Hay, M.

    2011-06-20

    The Defense Waste Processing Facility (DWPF) is pursuing alternative reductants/flowsheets to increase attainment to meet closure commitment dates. In fiscal year 2009, SRNL evaluated several options and recommended the further assessment of the nitric/formic/glycolic acid flowsheet. SRNL is currently performing testing with this flowsheet to support the DWPF down-select of alternate reductants. As part of the evaluation, SRNL was requested to determine the physical properties of formic and glycolic acid blends. Blends of formic acid in glycolic acid were prepared and their physical properties tested. Increasing amounts of glycolic acid led to increases in blend density, viscosity and surface tension as compared to the 90 wt% formic acid that is currently used at DWPF. These increases are small, however, and are not expected to present any difficulties in terms of processing. The effect of sulfur impurities in technical grade glycolic acid was studied for its impact on DWPF glass quality. While the glycolic acid specification allows for more sulfate than the current formic acid specification, the ultimate impact is expected to be on the order of 0.03 wt% sulfur in glass. Note that lower sulfur content glycolic acid could likely be procured at some increased cost if deemed necessary. A paper study on the effects of radiation on glycolic acid was performed. The analysis indicates that substitution of glycolic acid for formic acid would not increase the radiolytic production rate of H{sub 2} and cause an adverse effect in the SRAT or SME process. It has been cited that glycolic acid solutions that are depleted of O{sub 2} when subjected to large radiation doses produced considerable quantities of a non-diffusive polymeric material. Considering a constant air purge is maintained in the SRAT and the solution is continuously mixed, oxygen depletion seems unlikely, however, if this polymer is formed in the SRAT solution, the rheology of the solution may be affected and

  6. Urban and semi-rural observations of carboxylic acids and carbonyls

    NASA Astrophysics Data System (ADS)

    Granby, Kit; Christensen, Carsten S.; Lohse, Christian

    In a busy street in Central Copenhagen winter mean concentrations (ppbv) were for formic acid, (0.7 ± 0.3); acetic acid, (1.2 ± 0.5); formaldehyde, (2.6 ± 0.7); acetaldehyde, (1.0 ± 0.7); and acetone, (1.0 ± 0.5). Simultaneous measurements at a semi-rural site 30 km west of Copenhagen showed mean concentrations (ppbv) of: formic acid, (0.6 ± 0.3); acetic acid, (1.0 ± 0.5); formaldehyde, (0.9 ± 0.5); acetaldehyde, (0.7 ± 0.4); and acetone, (0.9 ± 0.4). The similar concentrations of formic acid and acetic acid at the two sites in Denmark when NO y concentrations were one order of magnitude lower at the semi-rural site indicate that primary emission from automobiles was not an important source of the carboxylic acids. In a busy street in Brussels, Belgium summer mean concentrations (ppbv) were for formic acid, (3.6 ± 1.6) and acetic acid, (4.0 ± 2.0). Weaker diurnal variation of formic acid and acetic acid than of the directly emitted NO y and CO in both Copenhagen and Brussels further support sources of the carboxylic acids other than car traffic. For formaldehyde the strong correlations with gas NO y and CO indicate that direct emission from automobile is a source. Acetone shows similar concentrations at the urban and semirural sites and weak correlations with CO and gas NO y which indicate other sources than traffic emission. For acetone and the carboxylic acids the similar concentrations at the urban and semi-rural site may be explained by a regional photochemical source, i.e. oxidation of reactive hydrocarbons in polluted air masses carried to the region by long-range transport.

  7. Molar extinction coefficients of some fatty acids

    NASA Astrophysics Data System (ADS)

    Sandhu, G. K.; Singh, Kulwant; Lark, B. S.; Gerward, L.

    2002-10-01

    The attenuation of gamma rays in some fatty acids, viz. formic acid (CH 2O 2), acetic acid (C 2H 4O 2), propionic acid (C 3H 6O 2), butyric acid (C 4H 8O 2), n-hexanoic acid (C 6H 12O 2), n-caprylic acid (C 8H 16O 2), lauric acid (C 12H 24O 2), myristic acid (C 14H 28O 2), palmitic acid (C 16H 32O 2), oleic acid (C 18H 34O 2) and stearic acid (C 18H 36O 2), has been measured at the photon energies 81, 356, 511, 662, 1173 and 1332 keV. Experimental values for the molar extinction coefficient, the effective atomic number and the electron density have been derived and compared with theoretical calculations. There is good agreement between experiment and theory.

  8. ADS pilot program Plan

    NASA Technical Reports Server (NTRS)

    Clauson, J.; Heuser, J.

    1981-01-01

    The Applications Data Service (ADS) is a system based on an electronic data communications network which will permit scientists to share the data stored in data bases at universities and at government and private installations. It is designed to allow users to readily locate and access high quality, timely data from multiple sources. The ADS Pilot program objectives and the current plans for accomplishing those objectives are described.

  9. The role of low molecular weight organic acids on controlling pH in coastal sea water

    NASA Astrophysics Data System (ADS)

    Ding, H.

    2015-12-01

    Series investigation of the Jiaozhou Bay, China, observed existences of three low molecular weight organic acids (LMWOAs), including lactic acid, acetic acid and formic acid, with high concentration in the sea water. Generally, their amount accounted for about 20% of DOC in the sea water of the bay. Human activities around the bay were considered as the major source of the LMWOAs. Also, long term detection showed that the pH value in the Jiaozhou Bay was lower than that in the adjacent Yellow Sea. On average, the difference of pH values between the bay and the Yellow was about 0.2. Due to higher concentrations of the LMWOAs, their contribution to lower pH value of the bay should not be ignored. To validate the effect of LMWOAs on the pH value of the bay, a new software was developed to calculate the pH value in the sea water samples based on alkalinity by adding three items of the three organic acids in the expression. Compared to the traditional pH calculating software, the new software could improve the calculating results significantly. Our results confirmed that LMWOAs was an important control factor to adjust pH values in coastal area.

  10. Innovations Without Added Costs

    ERIC Educational Resources Information Center

    Cereghino, Edward

    1974-01-01

    There is no question that we are in a tight money market, and schools are among the first institutions to feel the squeeze. Therefore, when a plan is offered that provides for innovations without added costs, its something worth noting. (Editor)

  11. What Value "Value Added"?

    ERIC Educational Resources Information Center

    Richards, Andrew

    2015-01-01

    Two quantitative measures of school performance are currently used, the average points score (APS) at Key Stage 2 and value-added (VA), which measures the rate of academic improvement between Key Stage 1 and 2. These figures are used by parents and the Office for Standards in Education to make judgements and comparisons. However, simple…

  12. Introducing ADS Labs

    NASA Astrophysics Data System (ADS)

    Accomazzi, Alberto; Henneken, E.; Grant, C. S.; Kurtz, M. J.; Di Milia, G.; Luker, J.; Thompson, D. M.; Bohlen, E.; Murray, S. S.

    2011-05-01

    ADS Labs is a platform that ADS is introducing in order to test and receive feedback from the community on new technologies and prototype services. Currently, ADS Labs features a new interface for abstract searches, faceted filtering of results, visualization of co-authorship networks, article-level recommendations, and a full-text search service. The streamlined abstract search interface provides a simple, one-box search with options for ranking results based on a paper relevancy, freshness, number of citations, and downloads. In addition, it provides advanced rankings based on collaborative filtering techniques. The faceted filtering interface allows users to narrow search results based on a particular property or set of properties ("facets"), allowing users to manage large lists and explore the relationship between them. For any set or sub-set of records, the co-authorship network can be visualized in an interactive way, offering a view of the distribution of contributors and their inter-relationships. This provides an immediate way to detect groups and collaborations involved in a particular research field. For a majority of papers in Astronomy, our new interface will provide a list of related articles of potential interest. The recommendations are based on a number of factors, including text similarity, citations, and co-readership information. The new full-text search interface allows users to find all instances of particular words or phrases in the body of the articles in our full-text archive. This includes all of the scanned literature in ADS as well as a select portion of the current astronomical literature, including ApJ, ApJS, AJ, MNRAS, PASP, A&A, and soon additional content from Springer journals. Fulltext search results include a list of the matching papers as well as a list of "snippets" of text highlighting the context in which the search terms were found. ADS Labs is available at http://adslabs.org

  13. Microbial production of value-added nutraceuticals.

    PubMed

    Wang, Jian; Guleria, Sanjay; Koffas, Mattheos A G; Yan, Yajun

    2016-02-01

    Nutraceuticals are important natural bioactive compounds that confer health-promoting and medical benefits to humans. Globally growing demands for value-added nutraceuticals for prevention and treatment of human diseases have rendered nutraceuticals a multi-billion dollar market. However, supply limitations and extraction difficulties from natural sources such as plants, animals or fungi, restrict the large-scale use of nutraceuticals. Metabolic engineering via microbial production platforms has been advanced as an eco-friendly alternative approach for production of value-added nutraceuticals from simple carbon sources. Microbial platforms like the most widely used Escherichia coli and Saccharomyces cerevisiae have been engineered as versatile cell factories for production of diverse and complex value-added chemicals such as phytochemicals, prebiotics, polysaccaharides and poly amino acids. This review highlights the recent progresses in biological production of value-added nutraceuticals via metabolic engineering approaches. PMID:26716360

  14. Multiple-acid equilibria in adsorption of carboxylic acids from dilute aqueous solution

    SciTech Connect

    Husson, S.M.; King, C.J.

    1999-02-01

    Equilibria were measured for adsorption of carboxylic acids from aqueous, binary-acid mixtures of lactic and succinic acids and acetic and formic acids onto basic polymeric sorbents. The experimentally determined adsorption isotherms compared well with model predictions, confirming that simple extensions from adsorption of individual acids apply. Fixed-bed studies were carried out that establish the efficacy of chromatographic fractionation of lactic and succinic acids using basic polymeric sorbents. Finally, sequential thermal and solvent regeneration of lactic and acetic acid-laden sorbents was investigated as a method to fractionate among coadsorbed volatile and nonvolatile acids. Essentially complete removal of the acetic acid from the acid-laden sorbent was achieved by vaporization under the conditions used; a small amount of loss of lactic acid (about 11%) was observed.

  15. Organic acids emissions from natural-gas-fed engines

    NASA Astrophysics Data System (ADS)

    Zervas, Efthimios; Tazerout, Mohand

    A natural-gas-fed spark-ignition engine, operating under lean conditions, is used for the study of the organic acids exhaust emissions. These pollutants are collected by passing a sample of exhaust gas into deionised water. The final solution is directly analysed by HPLC/UV at 204 nm. Only formic acid is emitted in detectable concentration under the experimental conditions used. Its concentration decreases with the three engine operating parameters studied: spark advance, volumetric efficiency and fuel/air equivalence ratio. Exhaust formic acid concentration is also linked with exhaust oxygen concentration and exhaust temperature. A comparison with other engines (SI engines fed with gasoline and compression ignition engines) from bibliographic data proves that natural-gas-fed engines emit less organic acids than the other two types of engines.

  16. Effect of Chitosan Dissolved in Different Acids on its Ability to Control Postharvest Gray Mold of Table Grape

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Chitosan is a natural biopolymer that must be dissolved in an acid solution to activate its antimicrobial and eliciting properties. Among 15 acids, chitosan dissolved in 1% solutions of acetic, L-ascorbic, formic, L-glutamic, hydrochloric, lactic, maleic, malic, phosphorous, and succinic. Chitosan s...

  17. Two Virasoro symmetries in stringy warped AdS3

    NASA Astrophysics Data System (ADS)

    Compère, Geoffrey; Guica, Monica; Rodriguez, Maria J.

    2014-12-01

    We study three-dimensional consistent truncations of type IIB supergravity which admit warped AdS3 solutions. These theories contain subsectors that have no bulk dynamics. We show that the symplectic form for these theories, when restricted to the non-dynamical subsectors, equals the symplectic form for pure Einstein gravity in AdS3. Consequently, for each consistent choice of boundary conditions in AdS3, we can define a consistent phase space in warped AdS3 with identical conserved charges. This way, we easily obtain a Virasoro × Virasoro asymptotic symmetry algebra in warped AdS3; two different types of Virasoro × Kač-Moody symmetries are also consistent alternatives.

  18. Evidence of rapid production of organic acids in an urban air mass

    NASA Astrophysics Data System (ADS)

    Veres, Patrick R.; Roberts, James M.; Cochran, Anthony K.; Gilman, Jessica B.; Kuster, William C.; Holloway, John S.; Graus, Martin; Flynn, James; Lefer, Barry; Warneke, Carsten; de Gouw, Joost

    2011-09-01

    Gas-phase acids (nitric, formic, acrylic, methacrylic, propionic, and pyruvic/butryic acid) were measured using negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) in Pasadena, CA as part of the CalNex 2010 (Research at the Nexus of Air Quality and Climate Change) study in May-June 2010. Organic acid concentrations ranged from a few parts per trillion by volume (pptv) to several parts per billion by volume (ppbv), with the largest concentrations observed for formic and propionic acids. Photochemically processed urban emissions transported from Los Angeles were frequently sampled during the day. Analysis of transported emissions demonstrates a strong correlation of organic acid concentrations with both nitric acid and odd oxygen (Ox = O3 + NO2) showing that the organic acids are photochemically and rapidly produced from urban emissions.

  19. [Determination of twelve chemical drugs illegally added in herbal tea by ultra high performance liquid chromatography-tandem mass spectrometry coupled with modified QuEChERS].

    PubMed

    Song, Ningning; Zhang, Keming; Liu, Xianghong; Sang, Tong; Sun, Yu; Teng, Nanyan

    2015-10-01

    An ultra high performance liquid chromatography-tandem mass spectrometry method with modified QuEChERS procedure for sample preparation was developed for the simultaneous determination of 12 chemical drugs (chlorpheniramine, piroxicam, α-asarone etc) illegally added in herbal tea. The samples were extracted with acetonitrile, purified with QuEChERS procedure and filtrated by 0.22 μm microporous filters. The separation was carried on an XBridge BEH C18 column (100 mm x 2.1 mm, 3.5 μm) by a gradient elution using acetonitrile/0.1% (v/v) formic acid aqueous solution as mobile phases. The analytes were detected by tandem mass spectrometry with positive electrospray ionization (ESI+) in multiple reaction monitoring (MRM) mode, and quantified by external standard calibration method. The correlation coefficients of the standard calibration curves for the 12 analytes were all above 0.997. The limits of detection ranged from 0.1 μg/L to 2.1 μg/L, and the limits of quantification ranged from 0.4 g/L to 8.0 μg/L. The average recoveries of the 12 analytes spiked at three levels in blank samples ranged from 62.7% to 95.2% with the RSDs from 1.3% to 10.8%. The samples bought from markets were screened, and some of the samples showed positive for these analytes. The method developed is easy to operate, sensitive, and with good purification effect. It can be applied to the rapid determination of the 12 chemical drugs illegally added in herbal tea. PMID:26930958

  20. Leading Change, Adding Value.

    PubMed

    Evans, Nick

    2016-09-12

    Essential facts Leading Change, Adding Value is NHS England's new nursing and midwifery framework. It is designed to build on Compassion in Practice (CiP), which was published 3 years ago and set out the 6Cs: compassion, care, commitment, courage, competence and communication. CiP established the values at the heart of nursing and midwifery, while the new framework sets out how staff can help transform the health and care sectors to meet the aims of the NHS England's Five Year Forward View. PMID:27615573

  1. Organic Acids Over Equatorial Africa: Results from DECAFE 88

    NASA Astrophysics Data System (ADS)

    Helas, Günter; Bingemer, Heinz; Andreae, Meinrat O.

    1992-04-01

    Gaseous short chain organic acids were measured during the dry season (February) in and above the rain forest of the northern Congo. Samples were taken at ground level and during several flights up to 4 km altitude. The organic acids were concentrated from the atmosphere by using "mist scrubbers," which expose a mist of deionized water to the air to be probed. The organic acids absorbed in the water were subsequently analyzed by ion chromatography. Formic, acetic, and pyruvic acids were identified in the samples. At ground level, average mixing ratios of gaseous formic and acetic acid of 0.5±0.6 and 0.6±0.7 parts per billion by volume (ppbv) (1 s), respectively, were found. Boundary layer mixing ratios, however, were significantly higher (3.7±1.0 and 2.7±0.9 ppbv). This indicates a downward net flux of these atmospheric trace components from the boundary layer to the surface. Free tropospheric samples taken above the cloud convection layer show lower mixing ratios again (0.9±0.3 and 0.7±0.1 ppbv). On the basis of this vertical distribution, direct emission by vegetation is not considered to be the dominant source. Biomass burning and photochemical oxidation of biogenic precursors are the major processes contributing to the enhancement of organic acids observed in the boundary layer. The organic acids parallel the profiles of ozone and CO, which suggests that their generation processes are closely related. Pyruvic acid is not correlated with formic acid, indicating that the oxidation of isoprene is not of major importance. In emissions from biomass fires, CO correlates well with formic and acetic acid, and thus some of the enhancement of organic acids in the boundary layer can be explained due to burning. However, an additional gas phase source for organic acids must exist to explain the observed ratio of formic to acetic acid. This is most likely the ozonolysis of olefins which were released as pyrolysis products from biomass burning.

  2. Indoor air chemistry: Formation of organic acids and aldehydes

    SciTech Connect

    Zhang, J.; Lioy, P.J. ||; Wilson, W.E.

    1994-12-31

    Laying emphasis on the formation of aldehydes and organic acids, the study has examined the gas-phase reactions of ozone with unsaturated VOCs. The formation of formaldehyde and formic acid was observed for all the three selected unsaturated VOCs: styrene, limonene, and 4-vinylcyclohexene. In addition, benzaldehyde was detected in the styrene-ozone-air reaction system, and acetic acid was also found in limonene-ozone-air system. The study has also examined the gas-phase reactions among formaldehyde, ozone, and nitrogen dioxide and found the formation of formic acid. The nitrate radical was suggested to play an important role in converting formaldehyde into formic acid. Experiments for all the reactions were conducted by using a 4.3 m{sup 3} Teflon chamber. Since the conditions for the reactions were similar to those for indoor environments, the results from the study can be implicated to real indoor situations and can be employed to support the findings and suggestions from the previous studies: certain aldehydes and organic acids could be generated by indoor chemistry.

  3. Conversion of levulinic acid into γ-valerolactone using Fe3(CO)12: mimicking a biorefinery setting by exploiting crude liquors from biomass acid hydrolysis.

    PubMed

    Metzker, Gustavo; Burtoloso, Antonio C B

    2015-09-28

    The conversion of biomass-derived levulinic acid (LA) into gamma-valerolactone (GVL) using formic acid (FA) and Fe3(CO)12 as the catalyst precursor was achieved in 92% yield. To mimic a biorefinery setting, crude liquor (containing 20% LA) from the acid hydrolysis of sugarcane biomass in a pilot plant facility was directly converted into GVL in good yield (50%), without the need for isolating LA. PMID:26258183

  4. Dirac operator on fuzzy AdS2

    NASA Astrophysics Data System (ADS)

    Fakhri, Hossein; Imaanpur, Ali

    2003-03-01

    In this article we construct the chirality and Dirac operators on noncommutative AdS2. We also derive the discrete spectrum of the Dirac operator which is important in the study of the spectral triple associated to AdS2. It is shown that the degeneracy of the spectrum present in the commutative AdS2 is lifted in the noncommutative case. The way we construct the chirality operator is suggestive of how to introduce the projector operators of the corresponding projective modules on this space.

  5. An xp model on AdS2 spacetime

    NASA Astrophysics Data System (ADS)

    Molina-Vilaplana, Javier; Sierra, Germán

    2013-12-01

    In this paper we formulate the xp model on the AdS2 spacetime. We find that the spectrum of the Hamiltonian has positive and negative eigenvalues, whose absolute values are given by a harmonic oscillator spectrum, which in turn coincides with that of a massive Dirac fermion in AdS2. We extend this result to generic xp models which are shown to be equivalent to a massive Dirac fermion on spacetimes whose metric depend of the xp Hamiltonian. Finally, we construct the generators of the isometry group SO(2,1) of the AdS2 spacetime, and discuss the relation with conformal quantum mechanics.

  6. Experimental study of the hydrothermal reactivity of organic acids and acid anions: II. Acetic acid, acetate, and valeric acid

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.; Seewald, Jeffrey S.

    2003-10-01

    Organic acids and acid anions occur in substantial concentrations in many aqueous geologic fluids and are thought to take part in a variety of geochemical processes ranging from the transport of metals in ore-forming fluids to the formation of natural gas to serving as a metabolic energy source for microbes in subsurface habitats. The widespread occurrence of organic acids and their potential role in diverse geologic processes has led to numerous experimental studies of their thermal stability, yet there remain substantial gaps in our knowledge of the factors that control the rates and reaction pathways for the decomposition of these compounds under geologic conditions. In order to address some of these uncertainties, a series of laboratory experiments were conducted to examine the behavior of organic acids and acid anions under hydrothermal conditions in the presence of minerals. Reported here are results of experiments where aqueous solutions of acetic acid, sodium acetate, or valeric acid ( n-pentanoic acid) were heated at 325°C, 350 bars in the presence of the mineral assemblages hematite + magnetite + pyrite, pyrite + pyrrhotite + magnetite, and hematite + magnetite. The results indicate that aqueous acetic acid and acetate decompose by a combination of two reaction pathways: decarboxylation and oxidation. Both reactions are promoted by minerals, with hematite catalyzing the oxidation reaction while magnetite catalyzes decarboxylation. The oxidation reaction is much faster, so that oxidation dominates the decomposition of acetic acid and acetate when hematite is present. In contrast to previous reports that acetate decomposed more slowly than acetic acid, we found that acetate decomposed at slightly faster rates than the acid in the presence of minerals. Although longer-chain monocarboxylic acids are generally thought to decompose by decarboxylation, valeric acid appeared to decompose primarily by "deformylation" to 1-butene plus formic acid. Subsequent

  7. ADS Development in Japan

    NASA Astrophysics Data System (ADS)

    Kikuchi, Kenji

    2010-06-01

    Accelerator driven nuclear transmutation system has been pursued to have a clue to the solution of high-level radioactive waste management. The concept consists of super conducting linac, sub-critical reactor and the beam window. Reference model is set up to 800MW thermal power by using 1.5GeV proton beams with considerations multi-factors such as core criticality. Materials damage is simulated by high-energy particle transport codes and so on. Recent achievement on irradiation materials experiment is stated and the differences are pointed out if core burn-up is considered or not. Heat balance in tank-type ADS indicates the temperature conditions of steam generator, the beam widow and cladding materials. Lead-bismuth eutectics demonstration has been conducted. Corrosion depth rate was shown by experiments.

  8. Supersymmetric warped AdS in extended topologically massive supergravity

    NASA Astrophysics Data System (ADS)

    Deger, N. S.; Kaya, A.; Samtleben, H.; Sezgin, E.

    2014-07-01

    We determine the most general form of off-shell N=(1,1) supergravity field configurations in three dimensions by requiring that at least one off-shell Killing spinor exists. We then impose the field equations of the topologically massive off-shell supergravity and find a class of solutions whose properties crucially depend on the norm of the auxiliary vector field. These are spacelike-squashed and timelike-stretched AdS3 for the spacelike and timelike norms, respectively. At the transition point where the norm vanishes, the solution is null warped AdS3. This occurs when the coefficient of the Lorentz-Chern-Simons term is related to the AdS radius by μℓ=2. We find that the spacelike-squashed AdS3 can be modded out by a suitable discrete subgroup of the isometry group, yielding an extremal black hole solution which avoids closed timelike curves.

  9. The ensemble effect of formic acid oxidation on platinum-gold electrode studied by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Zhong, Wenhui; Qi, Yuanyuan; Deng, Mingsen

    2015-03-01

    The reaction mechanisms for HCOOH oxidation on a series of PtAu(111) alloy surfaces in the aqueous solution phase are investigated by density functional theory calculations. It is found that the dehydrogenation pathway of HCOOH oxidation occurs through the formation of formate with a barrier of 16.8 kcal mol-1 and requires at least one Pt atom on the surface. In contrast, the CO formation pathway proceeds through the dimerization with a barrier of 5.6 kcal mol-1, for which at least three Pt atoms with a non-equilateral structure are required. The calculated average electrostatic potential, charge density difference, Bader charge and partial density of states all show obvious charge transfer from the alloy surface Pt atoms to HCOOH molecules, indicating that Pt sites are the reaction active center. Different ensemble of Pt sites on PtAu(111) surfaces can have significant impact on the catalysis performance for HCOOH oxidation. The non-equilateral Pt site upon PtAu(111) should be avoided to eliminate CO poisoning effect on Pt-based catalysts.

  10. Formic and acetic acids in degradation products of plant volatiles elicit olfactory and behavorial responses from an insect vector

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Asian citrus psyllid, Diaphorina citri Kuwayama (Hemiptera: Liviidae) vectors the bacterial pathogen presumed to be the etiological agent of citrus greening disease, Huanglongbing (HLB), a major threat to citrus industry worldwide. We studied antennal and behavioral responses of Diaphorina citri...

  11. Effects of formic acid and phytase supplementation on digestibility and use of phosphorus and zinc in growing pigs.

    PubMed

    Blank, R; Naatjes, M; Baum, C; Köhling, K; Ader, P; Roser, U; Susenbeth, A

    2012-12-01

    Two studies, arranged according to a 4 × 4 Latin square design, were conducted to assess effects of dietary acidification on fungal 3-phytase (PHY) efficacy in growing pigs. In Exp. 1, effects of supplementing 500 units/kg feed of PHY and 4.7 g/kg HCOOH either alone or in combination on the use of P and Zn in growing pigs fed a pelleted diet based on wheat (Triticum aestivum), barley (Hordeum vulgare), and soybean (Glycine max) meal were investigated. In Exp. 2 the same dietary treatments were fed except that PHY supplementation was increased to 1000 units/kg. In both experiments, PHY supplementation increased (P < 0.05) P digestibility and retention. A PHY × HCOOH supplementation interaction on P balance was observed (P < 0.05), indicating that the combination of the additives may increase P digestibility and retention. Effects of HCOOH and PHY on Zn use followed a similar pattern. Supplementation of 1000 units/kg of PHY further increased P and Zn retention compared to supplementation of 500 units/kg. In conclusion, the present study indicated that HCOOH supplementation to diets with microbial PHY may increase PHY efficacy. PMID:23365333

  12. Acid effect on excited Auramine-O molecular rotor relaxations in solution and adsorbed on insulin fibrils

    NASA Astrophysics Data System (ADS)

    Simkovitch, R.; Akulov, K.; Erez, Y.; Amdursky, N.; Gepshtein, R.; Schwartz, T.; Huppert, D.

    2015-09-01

    Steady-state and time-resolved UV-Vis spectroscopy techniques were employed to study the non-radiative process of Auramine-O (AuO). We focused our attention on the ultrafast nonradiative decay of Auramine-O in water and on the acid effect on Auramine-O spectroscopy. We found that weak acids like formic acid shorten the excited-state decay times of both the emission and the transient pump-probe spectra of Auramine-O. We found three time domains in the relaxation of the excited states back to the ground state. In mixtures of acetic and formic acids, the three decay times associated with the relaxation process are shorter in the presence of formic acid in Auramine-O solutions. We qualitatively explain the very large non-radiative rate in water and in formic-acetic acid mixtures by a protic nonradiative model proposed by Sobolewski and Domcke. The steady-state emission spectrum of AuO adsorbed on insulin fibrils consists of two bands assigned to protonated and deprotonated forms and the emission intensity increases by three orders of magnitude. We conclude that the nonradiative process prevails in the liquid state, whereas when AuO is adsorbed on fibrils the nonradiative rate is reduced by three orders of magnitude and thus enables a slow ESPT process to occur.

  13. Nonequimolar Mixture of Organic Acids and Bases: An Exception to the Rule of Thumb for Salt or Cocrystal.

    PubMed

    Pratik, Saied Md; Datta, Ayan

    2016-08-01

    Formation of salt and/or cocrystal from organic acid-base mixtures has significant consequences in the pharmaceutical industry and its related intellectual property rights (IPR). On the basis of calculations using periodic dispersion corrected DFT (DFT-D2) on formic acid-pyridine adduct, we have demonstrated that an equimolar stoichiometric ratio (1:1) exists as a neutral cocrystal. On the other hand, the nonequimolar stoichiometry (4:1) readily forms an ionic salt. While the former result is in agreement with the ΔpKa rule between the base and the acid, the latter is not. Calculations reveal that, within the equimolar manifold (n:n; n = 1-4), the mixture exists as a hydrogen bonded complex in a cocrystal-like environment. However, the nonequimolar mixture in a ratio of 5:1 and above readily forms salt-like structures. Because of the cooperative nature of hydrogen bonding, the strength of the O-H···N hydrogen bond increases and eventually transforms into O(-)···H-N(+) (complete proton transfer) as the ratio of formic acid increases and forms salt as experimentally observed. Clearly, an enhanced polarization of formic acid on aggregation increases its acidity and, hence, facilitates its transfer to pyridine. Motion of the proton from formic acid to pyridine is shown to follow a relay mechanism wherein the proton that is far away from pyridine is ionized and is subsequently transferred to pyridine via hopping across the neutral formic acid molecules (Grotthuss type pathway). The dynamic nature of protons in the condensed phase is also evident for cocrystals as the barrier of intramolecular proton migration in formic acid (leading to tautomerism), ΔH(⧧)tautomer = 17.1 kcal/mol in the presence of pyridine is half of that in free formic acid (cf. ΔH(⧧)tautomer = 34.2 kcal/mol). We show that an acid-base reaction can be altered in the solid state to selectively form a cocrystal or salt depending on the strength and nature of aggregation. PMID:27400140

  14. 27 CFR 24.182 - Use of acid to correct natural deficiencies.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    .... Tartaric acid or malic acid, or a combination of tartaric acid and malic acid, may be added prior to or... acid, fumaric acid, malic acid, lactic acid or tartaric acid, or a combination of two or more of these... citric acid may be added to citrus fruit, juice or wine, only malic acid may......

  15. 27 CFR 24.182 - Use of acid to correct natural deficiencies.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    .... Tartaric acid or malic acid, or a combination of tartaric acid and malic acid, may be added prior to or... acid, fumaric acid, malic acid, lactic acid or tartaric acid, or a combination of two or more of these... citric acid may be added to citrus fruit, juice or wine, only malic acid may......

  16. Value Added in English Schools

    ERIC Educational Resources Information Center

    Ray, Andrew; McCormack, Tanya; Evans, Helen

    2009-01-01

    Value-added indicators are now a central part of school accountability in England, and value-added information is routinely used in school improvement at both the national and the local levels. This article describes the value-added models that are being used in the academic year 2007-8 by schools, parents, school inspectors, and other…

  17. Per aspirin ad astra...

    PubMed

    Hartung, Thomas

    2009-12-01

    Taking the 110th anniversary of marketing of aspirin as starting point, the almost scary toxicological profile of aspirin is contrasted with its actual use experience. The author concludes that we are lucky that, in 1899, there was no regulatory toxicology. Adding, for the purpose of this article, a fourth R to the Three Rs, i.e. Realism, three reality-checks are carried out. The first one comes to the conclusion that the tools of toxicology are hardly adequate for the challenges ahead. The second one concludes that, specifically, the implementation of the EU REACH system is not feasible with these tools, mainly with regard to throughput. The third one challenges the belief that classical alternative methods, i.e. replacing animal test-based tools one by one, is actually leading to a new toxicology - it appears to change only patches of the patchwork, but not to overcome any inherent limitations other than ethical ones. The perspective lies in the Toxicology for the 21st Century initiatives, which aim to create a new approach from the scratch, by an evidence-based toxicology and a global "Human Toxicology Programme". PMID:20105011

  18. Organics Characterization Of DWPF Alternative Reductant Simulants, Glycolic Acid, And Antifoam 747

    SciTech Connect

    White, T. L.; Wiedenman, B. J.; Lambert, D. P.; Crump, S. L.; Fondeur, F. F.; Papathanassiu, A. E.; Kot, W. K.; Pegg, I. L.

    2013-10-01

    The present study examines the fate of glycolic acid and other organics added in the Chemical Processing Cell (CPC) of the Defense Waste Processing Facility (DWPF) as part of the glycolic alternate flowsheet. Adoption of this flowsheet is expected to provide certain benefits in terms of a reduction in the processing time, a decrease in hydrogen generation, simplification of chemical storage and handling issues, and an improvement in the processing characteristics of the waste stream including an increase in the amount of nitrate allowed in the CPC process. Understanding the fate of organics in this flowsheet is imperative because tank farm waste processed in the CPC is eventually immobilized by vitrification; thus, the type and amount of organics present in the melter feed may affect optimal melt processing and the quality of the final glass product as well as alter flammability calculations on the DWPF melter off gas. To evaluate the fate of the organic compounds added as the part of the glycolic flowsheet, mainly glycolic acid and antifoam 747, samples of simulated waste that was processed using the DWPF CPC protocol for tank farm sludge feed were generated and analyzed for organic compounds using a variety of analytical techniques at the Savannah River National Laboratory (SRNL). These techniques included Ion Chromatography (IC), Gas Chromatography-Mass Spectrometry (GC-MS), Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), and Nuclear Magnetic Resonance (NMR) Spectroscopy. A set of samples were also sent to the Catholic University of America Vitreous State Laboratory (VSL) for analysis by NMR Spectroscopy at the University of Maryland, College Park. Analytical methods developed and executed at SRNL collectively showed that glycolic acid was the most prevalent organic compound in the supernatants of Slurry Mix Evaporator (SME) products examined. Furthermore, the studies suggested that commercially available glycolic acid contained minor amounts

  19. Electrospun homogeneous silk fibroin/poly (ɛ-caprolactone) nanofibrous scaffolds by addition of acetic acid for tissue engineering.

    PubMed

    Zhu, Jiang; Luo, Jingjing; Zhao, Xingyan; Gao, Junjiu; Xiong, Jie

    2016-09-01

    In this study, we investigated the phase separation phenomenon of silk fibroin/poly (ɛ-caprolactone) electrospinning solution to improve the performance of silk fibroin/poly (ɛ-caprolactone) electrospun nanofibers. It showed that phase separation does occur in just a few hours in the silk fibroin/poly (ɛ-caprolactone)/formic acid mixture solution. Acetic acid, small molecule nonsolvent for silk fibroin, was first introduced to silk fibroin/poly (ɛ-caprolactone)/formic acid solution, a homogeneous solution without separation for over several days was achieved after mixing for 5 h. The morphology and composition of the silk fibroin/poly (ɛ-caprolactone) and acetic acid-modified silk fibroin/poly (ɛ-caprolactone) fibrous scaffolds were examined by scanning electron microscopy, Fourier transform infrared spectroscopy and thermal gravimetric analyzer. Attachment and proliferation of mouse osteoblast MC3T3-E1 cells were tested by scanning electron microscopy and cytotoxity assay. The results indicated that the phase separation of silk fibroin/poly (ɛ-caprolactone) solution might led to inhomogeneous morphology and composition of the composite scaffolds, and the inhomogeneity of the silk fibroin/poly (ɛ-caprolactone) scaffolds with formic acid as solvent had a remarkable difference on cell adhesion and proliferation. In contrast, there was no significant difference among the silk fibroin/poly (ɛ-caprolactone) scaffolds with formic acid/acetic acid as solvent because of their good consistency in fiber morphology and composition. These obtained silk fibroin/poly (ɛ-caprolactone) nanofibers had small average diameter of 190 ± 40 nm. The obtained results proved that this study provided a facile and effective approach to achieve compositionally homogeneous silk fibroin/poly (ɛ-caprolactone) scaffolds with formic acid as solvent for effective applications. PMID:27422715

  20. Supergravity at the boundary of AdS supergravity

    NASA Astrophysics Data System (ADS)

    Amsel, Aaron J.; Compère, Geoffrey

    2009-04-01

    We give a general analysis of AdS boundary conditions for spin-3/2 Rarita-Schwinger fields and investigate boundary conditions preserving supersymmetry for a graviton multiplet in AdS4. Linear Rarita-Schwinger fields in AdSd are shown to admit mixed Dirichlet-Neumann boundary conditions when their mass is in the range 0≤|m|<1/2lAdS. We also demonstrate that mixed boundary conditions are allowed for larger masses when the inner product is “renormalized” accordingly with the action. We then use the results obtained for |m|=1/lAdS to explore supersymmetric boundary conditions for N=1 AdS4 supergravity in which the metric and Rarita-Schwinger fields are fluctuating at the boundary. We classify boundary conditions that preserve boundary supersymmetry or superconformal symmetry. Under the AdS/CFT dictionary, Neumann boundary conditions in d=4 supergravity correspond to gauging the superconformal group of the three-dimensional CFT describing M2-branes, while N=1 supersymmetric mixed boundary conditions couple the CFT to N=1 superconformal topologically massive gravity.