Sample records for alkali carbonate reactions

  1. Alkali Aggregate Reaction in Alkali Slag Cement Mortars

    Institute of Scientific and Technical Information of China (English)


    By means of "Mortar Bar Method",the ratio of cement to aggregate was kept as a constant 1∶2.25,the water-cement ratio of the mixture was 0.40,and six prism specimens were prepared for each batch of mixing proportions with dimensions of 10×10×60mm3 at 38±2℃ and RH≥95%, the influences of content and particle size of active aggregate, sort and content of alkali component and type of slag on the expansion ratios of alkali-activated slag cement(ASC) mortars due to alkali aggregate reaction(AAR) were studied. According to atomic absorption spectrometry,the amount of free alkali was measured in ASC mortars at 90d.The results show above factors affect AAR remarkably,but no dangerous AAR will occur in ASC system when the amount of active aggregate is below 15% and the mass fraction of alkali is not more than 5% (Na2O).Alkali participated in reaction as an independent component, and some hydrates containing alkali cations were produced, free alkalis in ASC system can be reduced enormously.Moreover,slag is an effective inhibitor, the possibility of generating dangerous AAR in ASC system is much lower at same conditions than that in ordinary Portland cement system.

  2. Effect of Mineral Admixtures on Alkali-Silica Reaction

    Institute of Scientific and Technical Information of China (English)

    ZHANG Chengzhi; WANG Aiqin


    The influence of silica fume,slag and fly ash on alkali-silica reaction under the condition of 70℃ is studied.The results show that silica,slag and fly ash may inhibit alkali-silica reaction only under suitable content.When the content is less than 10%,silica fume does not markedly influence the expansion of alkali-silica reaction.When the content is 15%-20%,silica fume only may delay the expansion of alkali-silica reaction.When the content is 30%-70%,slag may only delay the expansion of alkali-silica reaction,but cannot inhibit the expansion of alkali-silica reaction.When the content is 10%,fly ash does not markedly influence the expansion of alkali-silica reaction.When the content is 20%-30%,fly ash may only delay the expansion of alkali-silica reaction,but cannot inhibit the expansion of alkali-silica reaction.When the content is over 50%,it is possible that fly ash can inhibit effectively alkali-silica reaction.

  3. Effect of Pozzolanic Reaction Products on Alkali-silica Reaction

    Institute of Scientific and Technical Information of China (English)

    WEI Fengyan; LAN Xianghui; LV Yinong; XU Zhongzi


    The effect of fly ash on controlling alkali-silica reaction (ASR) in simulated alkali solution was studied. The expansion of mortar bars and the content of Ca(OH)2 in cement paste cured at 80 ℃ for 91 d were measured. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were employed to study the microstructure of C-S-H. TEM/energy dispersive spectroscopy (EDS) was then used to determine the composition of C-S-H. The pore structure of the paste was analyzed by mercury intrusion porosimetry (MIP). The results show that the contents of fly ash of 30% and 45% can well inhibit ASR. And the content of Ca(OH)2 decreases with the increase of fly ash. That fly ash reacted with Ca(OH)2 to produce C-S-H with a low Ca/Si molar ratio could bind more Na+ and K+ ions, and produce a reduction in the amount of soluble alkali available for ASR. At the same time, the C-S-H produced by pozzolanic reaction converted large pores to smaller ones (gel pores smaller than 10 nm) to densify the pore structure. Perhaps that could inhibit alkali transport to aggregate for ASR.

  4. Alkali-aggregate reactivity of typical siliceious glass and carbonate rocks in alkali-activated fly ash based geopolymers (United States)

    Lu, Duyou; Liu, Yongdao; Zheng, Yanzeng; Xu, Zhongzi; Shen, Xiaodong


    For exploring the behaviour of alkali-aggregate reactivity (AAR) in alkali-activated geopolymeric materials and assessing the procedures for testing AAR in geopolymers, the expansion behaviour of fly ash based geopolymer mortars with pure silica glass and typical carbonate rocks were studied respectively by curing at various conditions, i.e. 23°C and 38°C with relative humidity over 95%, immersed in 1M NaOH solution at 80°C. Results show that, at various curing conditions, neither harmful ASR nor harmful ACR was observed in geopolymers with the criteria specified for OPC system. However, with the change of curing conditions, the geopolymer binder and reactive aggregates may experience different reaction processes leading to quite different dimensional changes, especially with additional alkalis and elevated temperatures. It suggests that high temperature with additional alkali for accelerating AAR in traditional OPC system may not appropriate for assessing the alkali-aggregate reactivity behaviour in geopolymers designed for normal conditions. On the other hand, it is hopeful to control the dimensional change of geopolymer mortar or concrete by selecting the type of aggregates and the appropriate curing conditions, thus changing the harmful AAR in OPC into beneficial AAR in geopolymers and other alkali-activated cementitious systems.

  5. Influence of alkalis from different sources than cement in the evolution of alkali-silica reaction

    Directory of Open Access Journals (Sweden)

    Olague, C.


    Full Text Available A bibliographical revision of the existent literature allows showing symptoms of alkali-silica reaction (ASR in highways, and the practical and economic method uranyl acetate to confirm the presence of ASR. The existence of reaction in concrete pavements of Chihuahua City was verified by a visual observation of patterns cracks, examination of gel deposits and the presence of reactive materials. Considering that the cement used to construct this pavements with problems of ASR, was low alkalis cement, the research was devoted to study the influence of alkalis coming from different sources than cement in the evolution of reaction such as: a aggregates: gravel and sand, b mix water, c additives and d minerals additions The initial classification of cements like high and low alkalis concerned to ASR must be revised for accept the fact that there is not a unique maximum limit alkalis of cement under which the expansible reactivity cannot occur.

    Una revisión bibliográfica de la literatura existente permite mostrar las manifestaciones de reacción álcali-sílice (RAS en estructuras de carreteras y el método práctico y económico de acetato de uranilo para confirmar la presencia de RAS. La existencia de la reacción en pavimentos de hormigón de la ciudad de Chihuahua se pudo confirmar tras la observación visual de modelos de grietas, estudios de depósitos de gel y existencia de fuentes de materiales reactivos. Considerando que el cemento utilizado para construir los tramos de pavimento con problemas de RAS, era un cemento bajo en álcalis, se enfocó la investigación al estudio de la influencia de los álcalis provenientes de fuentes distintas al cemento en la evolución de la reacción tales como: a áridos gruesos y finos, b agua de mezclado, c aditivos y d adiciones minerales El concepto inicial de clasificación de cementos altos y bajos en álcalis con respecto a la RAS debe ser revisado para aceptar el hecho de que no hay un solo

  6. Spinel Metal Oxide-Alkali Carbonate-Based, Low-Temperature Thermochemical Cycles for Water Splitting and CO_2 Reduction


    Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E.


    A manganese oxide-based, thermochemical cycle for water splitting below 1000 °C has recently been reported. The cycle involves the shuttling of Na+ into and out of manganese oxides via the consumption and formation of sodium carbonate, respectively. Here, we explore the combinations of three spinel metal oxides and three alkali carbonates in thermochemical cycles for water splitting and CO_2 reduction. Hydrogen evolution and CO_2 reduction reactions of metal oxides with a given alkali carbona...

  7. Effect of Anti-freezing Admixtures on Alkali-silica Reaction in Mortars

    Institute of Scientific and Technical Information of China (English)

    LIU Junzhe; LI Yushun; LV Lihua


    The influence of anti-freezing admixture on the alkali aggregate reaction in mortar was analyzed with accelerated methods. It is confirmed that the addition of sodium salt ingredients of anti-freezing admixture accelerates the alkali silica reaction to some extent, whereas calcium salt ingredient of anti-freezing admixture reduces the expansion of alkali silica reaction caused by high alkali cement. It is found that the addition of the fly ash considerably suppresses the expansion of alkali silica reaction induced by the anti-freezing admixtures.

  8. Alkali-silica reaction resistant concrete using pumice blended cement (United States)

    Ramasamy, Uma

    Durability of structures is a major challenge for the building industry. One of the many types of concrete deterioration that can affect durability is alkali-silica reaction (ASR). ASR has been found in most types of concrete structures, including dams, bridges, pavements, and other structures that are 20 to 50 years old. The degradation mechanism of ASR produces a gel that significantly expands in the presence of water as supplied from the surrounding environment. This expansion gel product can create high stresses and cracking of the concrete, which can lead to other forms of degradation and expensive structural replacement costs. The four essential factors that produce an expansive ASR gel in concrete are the presence of alkalis, siliceous aggregate, moisture, and free calcium hydroxide (CH). If concrete is starved of any one of these essential components, the expansion can be prevented. Reducing CH through the use of a supplementary cementitious material (SCM) such as natural pozzolan pumice is the focus of this research. By using a pozzolan, the amount of CH is reduced with time based on the effectiveness of the pozzolan. Many pozzolans exist, but one such naturally occurring pozzolanic material is pumice. This research focuses on determining the effect of a finely ground pumice as a SCM in terms of its resistance to ASR expansion, as well as improving resistance to other potential concrete durability mechanisms. In spite of having high alkali contents in the pumice, mixtures containing the SCM pumice more effectively mitigated the ASR expansion reaction than other degradation mechanisms. Depending on the reactivity of the aggregates and fineness of the pumice, 10-15% replacement of cement with the pumice was found to reduce the ASR expansion to the acceptable limits. The amount of CH remaining in the concrete was compared to the ASR expansion in order to improve understanding of the role of CH in the ASR reaction. Thermo-gravimetric analysis (TGA) and X

  9. Ultrafine microporous and mesoporous activated carbon fibers from alkali lignin



    A facile and sustainable approach has been successfully devised to fabricate ultrafine (100-500 nm) highly porous activated carbon fibers (ACFs) by electrospinning of aqueous solutions of predominantly alkali lignin (low sulfonate content) followed by simultaneous carbonization and activation at 850 °C under N2. Incorporating a polyethylene oxide (PEO) carrier with only up to one ninth of lignin not only enabled efficient electrospinning into fibers but also retained fibrous structures during...

  10. In situ alkali-silica reaction observed by x-ray microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kurtis, K.E.; Monteiro, P.J.M. [Univ. of California, Berkeley, CA (United States); Brown, J.T.; Meyer-Ilse, W. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)


    In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques available for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.

  11. Alkali-Silica Reaction Inhibited by LiOH and Its Mechanism

    Institute of Scientific and Technical Information of China (English)


    A high alkali reactive aggregate-zeolitization perlite was used to test the long-term effectiveness of LiOH in inhibiting alkali-silica reaction.In this paper,the rigorous conditions were designed that the mortar bars had been cured at 80℃ for 3 years after autoclaved 24 hours at 150℃.Under this condition,LiOH was able to inhibit the alkali-silica reaction long-term effectiveness.Not only the relationship between the molar ratio of n(Li)/(Na) and the alkali contents in systems was established, but also the governing mechanism of such effects was also studied by SEM.

  12. Effect of the Composite of Natural Zeolite and Fly Ash on Alkali-Silica Reaction

    Institute of Scientific and Technical Information of China (English)

    FENG Xiao-xin; FENG Nai-qian; HAN Dong


    The effect of the composite of natural zeolite and fly ash on alkali-silica reaction ( ASR ) was studied with natural alkali-reactive aggregate and quartz glass aggregate respecthvely. The expansive experiment of mortar bar and concrete prism was completed. The results show that ASR can be suppressed effectively by the composite of natural zeolite and fly ash.

  13. Alkali metal mediated C-C bond coupling reaction. (United States)

    Tachikawa, Hiroto


    Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2](-) was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

  14. Assessment of concrete bridge decks with alkali silica reactions

    DEFF Research Database (Denmark)

    Eriksen, Kirsten; Jansson, Jacob; Geiker, Mette Rica


    Based on investigations of concrete from an approximately 40 years old bridge a procedure to support the management of maintenance and repair of alkali silica damaged bridges is proposed. Combined petrography and accelerated expansion testing were undertaken on cores from the Bridge at Skovdiget......, Bagsværd, Denmark to provide information on the damage condition as well as the residual reactivity of the concrete. The Danish Road Directory’s guidelines for inspection and assessment of alkali silica damaged bridges will be briefly presented, and proposed modifications will be describe...

  15. Recovery of alkali and alumina from Bayer red mud by the calcification-carbonation method (United States)

    Zhu, Xiao-feng; Zhang, Ting-an; Wang, Yan-xiu; Lü, Guo-zhi; Zhang, Wei-guang


    Red mud produced in the Bayer process is a hazardous solid waste because of its high alkalinity; however, it is rich in valuable components such as titanium, iron, and aluminum. In this study, a novel calcification-carbonation method was developed to recover alkali and alumina from Bayer red mud under mild reaction conditions. Batch experiments were performed to evaluate the potential effects of important parameters such as temperature, amount of CaO added, and CO2 partial pressure on the recovery of alkali and alumina. The results showed that 95.2% alkali and 75.0% alumina were recovered from red mud with decreases in the mass ratios of Na2O to Fe2O3 and of Al2O3 to Fe2O3 from 0.42 and 0.89 to 0.02 and 0.22, respectively. The processed red mud with less than 0.5wt% Na2O can potentially be used as a construction material.

  16. Chemical modelling of Alkali Silica reaction: Influence of the reactive aggregate size distribution

    Energy Technology Data Exchange (ETDEWEB)

    Poyet, S. [CEA Saclay, DEN/DANS/DPC/SCCME/LECBA, F-91191 Gif Sur Yvette, (France); Sellier, A. [UPS, LMDC, INSA Toulouse, F-33077 Bordeaux 4, (France); Capra, B. [Oxand SA, F-77210 Avon (France); Foray, G. [Univ Lyon 1, L2MS, PETRA GC, F-69622 Villeurbanne (France); Torrenti, J.M. [IRSN, F-92262 Fontenay Aux Roses (France); Cognon, H. [EdF/DER Les Renardieres, F-77818 Moret Sur Loing (France); Bourdarot, E. [CIH Savoie Technolac, F-73373 Le Bourget du Lac (France)


    This article presents a new model which aims at predicting the expansion induced by Alkali Silica Reaction (ASR) and describing the chemical evolution of affected concretes. It is based on the description of the transport and reaction of alkalis and calcium ions within a Relative Elementary Volume (REV). It takes into account the influence of the reactive aggregate size grading on ASR, i.e. the effect of the simultaneous presence of different sized reactive aggregates within concrete. The constitutive equations are detailed and fitted using experimental results. Results from numerical simulations are presented and compared with experiments. (authors)

  17. Effect of Grain Size and Reaction Time in Characterisation of Aggregates for Alkali Silica Reaction Using Chemical Method

    Directory of Open Access Journals (Sweden)

    R.P. Pathak


    Full Text Available Concrete can deteriorate as a result of alkali aggregate reaction, an interaction between alkalis present in alkaline pore solution originating from the Portland cement and reactive minerals in certain types of aggregates. Potential reactivity of aggregates with regard to alkalis present in concrete mix can be determined by Mortar Bar method, Chemical Method and Petrographic analysis. Of these the chemical method though is quick and does not require a large quantity of material for testing yet have its own inherent limitations. It does not ensure completion of reaction as the observations are limited to 24hour only and also does not assess the effect of varying the combination of coarse and fine aggregates. A study on chemical method by allowing the reaction for a prolonged time up to 96 hours and also on different grain size ranged matrix was carried at Central Soil and Materials Research Station, New Delhi. Simultaneously the test results of the modified method are compared to the existing Mortar Bar method, Chemical Method and Petrographic analysis The outcome of the studies clearly reflects that the grain size play an important role in the reaction, the reaction time has a demarked impact on reactivity, in the cases having a high value of silica release the choice of reduction in alkalinity as an indicator of degree of reaction is not reliable, instead measuring remaining Na2O concentration in Sodium hydroxide solution after the reaction seems to be much more meaningful in justifying the silica release.

  18. Experimental Investigation of CFRP Confined Columns Damaged by Alkali Aggregate Reaction

    Directory of Open Access Journals (Sweden)

    Siti Radziah Abdullah


    Full Text Available Fiber reinforced polymer is the most effective repair material in use to enhance the strength and ductility of deteriorated reinforced concrete columns. Often, fiber reinforced polymer (FRP provides passive confinement to columns until the dilation and cracking of concrete occurs. In the case of concrete suspected of Alkali Aggregate Reaction (AAR where concrete undergoes expansion, FRP wrap provides active confinement to the expanded concrete. In this study, the performance of carbon fiber reinforced polymer (CFRP wrapped columns damaged by AAR is evaluated based on the number of FRP layers and the time of the polymer application which provides two types of confinement: active or passive. The columns were tested under axial compression to evaluate the residual strength of the columns in comparison with unwrapped columns. The results reveal that the strength of the wrapped columns is enhanced with an increase in the number of CFRP layers. The strength of the columns under passive confinement is higher than the columns under active confinement. Under active confinement, early CFRP wrapping leads to improvement in the strength of the columns.

  19. [Surface characteristics of alkali modified activated carbon and the adsorption capacity of methane]. (United States)

    Zhang, Meng-Zhu; Li, Lin; Liu, Jun-Xin; Sun, Yong-Jun; Li, Guo-Bin


    Coconut shell based activated carbon was modified by alkali with different concentrations. The surface structures of tested carbons were observed and analyzed by SEM and BET methods. Boehm's titration and SEM/EDS methods were applied to assay the functional groups and elements on the carbon surface. The adsorption of methane on tested carbons was investigated and adsorption behavior was described by the adsorption isotherms. Results showed that surface area and pore volume of modified carbon increased and surface oxygen groups decreased as the concentration of the alkali used increased, with no obvious change in pore size. When concentration of alkali was higher than 3.3 mol x L(-1), the specific surface area and pore volume of modified carbon was larger than that of original carbon. Methane adsorption capacity of alkali modified carbon increased 24%. Enlargement of surface area and pore volume, reduction of surface oxygen groups will benefit to enhance the methane adsorption ability on activated carbon. Adsorption behavior of methane followed the Langmuir isotherm and the adsorption coefficient was 163.7 m3 x mg(-1).

  20. Reactions between cold methyl halide molecules and alkali-metal atoms. (United States)

    Lutz, Jesse J; Hutson, Jeremy M


    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH3X + A → CH3 + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  1. Influence of granitic aggregates from Northeast Brazil on the alkali-aggregate reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gomes Neto, David de Paiva; Santana, Rodrigo Soares de; Barreto, Ledjane Silva, E-mail: [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil). Dept. de Ciencias dos Materiais e Engenharia; Conceicao, Herbert; Lisboa, Vinicios Anselmo Carvalho [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil). Dept. de Geologia


    The alkali-aggregate reaction (AAR) in concrete structures is a problem that has concerned engineers and researchers for decades. This reaction occurs when silicates in the aggregates react with the alkalis, forming an expanded gel that can cause cracks in the concrete and reduce its lifespan. The aim of this study was to characterize three coarse granitic aggregates employed in concrete production in northeastern Brazil, correlating petrographic analysis with the kinetics of silica dissolution and the evolution of expansions in mortar bars, assisted by SEM/EDS, XRD, and EDX. The presence of grains showing recrystallization into individual microcrystalline quartz subgrains was associated with faster dissolution of silica and greater expansion in mortar bars. Aggregates showing substantial deformation, such as stretched grains of quartz with strong undulatory extinction, experienced slower dissolution, with reaction and expansion occurring over longer periods that could not be detected using accelerated tests with mortar bars. (author)

  2. Fluid Composititon and Carbon & Oxygen Isotope Geochemistry of Cenozoic Alkali Basalts in Eastern China

    Institute of Scientific and Technical Information of China (English)

    张铭杰; 王先彬; 等


    The fluid compositions of Cenozoic alkali basalts in eastern China have been determined by the pyrolysis-MS method,meanwhile the carbon and oxygen isotopic compositions of CO2 released from these samples at different heating temperatures have been analyzed by the vacuum step-heating method.The data show the volatiole heterogeneity in upper-mantle sources and different evolution trends of alkali basaltic magmas in eastern China,and these alkali basaltic magmas may be generated in the oxidizing milieu,as compared with mantle-derived xenoliths in these alkali basalts,and exotic volatile components were mixed into these magmas in the process of their formation and development.

  3. Biodiesel synthesis from cottonseed oil using homogeneous alkali catalyst and using heterogeneous multi walled carbon nanotubes: Characterization and blending studies

    Directory of Open Access Journals (Sweden)

    A. Arun Shankar


    Full Text Available The trans-esterification of cottonseed oil using strong alkali catalyst and using multi walled carbon nano tubes as catalyst to produce biodiesel was studied. The interaction effects of various factors such as temperature, amount of alkali used, alcohol to oil ratio and reaction time on yield of biodiesel were studied. The maximum yield of 95% biodiesel was obtained. The biodiesel produced was characterized using FT-IR spectral analysis and GC–MS analysis to ascertain the various functional groups and compounds available in it. The properties of biodiesel using homogeneous alkali catalyst and heterogeneous multi walled carbon nanotubes such as calorific value (36.18 MJ/kg, 33.78 MJ/kg, flash point (160 °C, 156 °C and other properties such as viscosity, cloud point, pour point and density were found to determine the quality of biodiesel produced. The studies were done by blending the biodiesel produced with diesel and properties of blended samples were estimated to ascertain the use of blended samples in internal combustion engines.

  4. Winning the battles on AAR[Alkali aggregate reaction in dams

    Energy Technology Data Exchange (ETDEWEB)

    Wood, J.


    This article discusses work carried out on four locks on the St. Lawrence Seaway to deal with the alkali aggregate reaction (AAR) in the concrete, on the Mactaquac dam on Canada's St John river which showed evidence of AAR, and also on the Paula Alfonso IV dam in Brazil where cracking was observed in concrete structures near the generators. The pattern of natural cracking is examined, and the source of the problem is identified. The use of admixtures to alleviate the problem is explored, and the utilisation of flyash, waste cement, silica fume, and lithium as concrete constituents is considered. New tests available using powdered rock flour aggregate to decrease alkali concentrations and improve cement workability are described.

  5. Assessment of Alkali-Silica Reaction Damage in Mortars with Nonlinear Ultrasonic Techniques (United States)

    Chen, J.; Jayapalan, A. R.; Kurtis, K. E.; Kim, J.-Y.; Jacobs, L. J.


    In this work, a nonlinear ultrasonic modulation technique is employed to assess the damage state of portland cement mortar samples induced by alkali-silica reaction (ASR). Due to the nonlinear interaction of propagating waves caused by distributed microcracks that are agitated from its equilibrium state, the ultrasonic responses of samples produce sideband frequencies around the frequency of propagating waves. The amplitude of the sidebands depends on the amplitude of the input signals and is particularly sensitive to the state of damage evolved in the sample. Therefore, the development of internal microcracks with increasing duration of exposure to aggressive conditions can be quantitatively related to the variation of external ultrasonic measurements. The ultrasonic results are compared with results from standard ASR expansion measurements (ASTM C 1260), and a proportionally increasing relation was found in the early stages. In addition, aggregates with different alkali-reactivity (i.e., low reactivity or high reactivity) were examined in a similar manner. The results indicate that the nonlinear parameter obtained from ultrasonic tests directly reflects the difference of aggregate reactivity. This clearly indicates that the developed nonlinear ultrasonic method is potentially a good alternative for a more rapid and still reliable assessment of aggregate alkali-reactivity.

  6. Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation

    Energy Technology Data Exchange (ETDEWEB)

    Bernal, Susan A., E-mail: [Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010 (Australia); Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom); Provis, John L., E-mail: [Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010 (Australia); Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom); Walkley, Brant; San Nicolas, Rackel [Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010 (Australia); Gehman, John D. [School of Chemistry and Bio21 Institute, The University of Melbourne, Victoria 3010 (Australia); Brice, David G.; Kilcullen, Adam R. [Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010 (Australia); Zeobond Pty Ltd, P.O. Box 23450, Docklands, Victoria 8012 (Australia); Duxson, Peter [Zeobond Pty Ltd, P.O. Box 23450, Docklands, Victoria 8012 (Australia); Deventer, Jannie S.J. van [Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010 (Australia); Zeobond Pty Ltd, P.O. Box 23450, Docklands, Victoria 8012 (Australia)


    Binders formed through alkali-activation of slags and fly ashes, including ‘fly ash geopolymers’, provide appealing properties as binders for low-emissions concrete production. However, the changes in pH and pore solution chemistry induced during accelerated carbonation testing provide unrealistically low predictions of in-service carbonation resistance. The aluminosilicate gel remaining in an alkali-activated slag system after accelerated carbonation is highly polymerised, consistent with a decalcification mechanism, while fly ash-based binders mainly carbonate through precipitation of alkali salts (bicarbonates at elevated CO{sub 2} concentrations, or carbonates under natural exposure) from the pore solution, with little change in the binder gel identifiable by nuclear magnetic resonance spectroscopy. In activated fly ash/slag blends, two distinct gels (C–A–S–H and N–A–S–H) are formed; under accelerated carbonation, the N–A–S–H gel behaves comparably to fly ash-based systems, while the C–A–S–H gel is decalcified similarly to alkali-activated slag. This provides new scope for durability optimisation, and for developing appropriate testing methodologies. -- Highlights: •C-A-S-H gel in alkali-activated slag decalcifies during accelerated carbonation. •Alkali-activated fly ash gel changes much less under CO{sub 2} exposure. •Blended slag-fly ash binder contains two coexisting gel types. •These two gels respond differently to carbonation. •Understanding of carbonation mechanisms is essential in developing test methods.

  7. Study of effect of electric arc furnace slag on expansion of mortars subjected to alkali-aggregate reaction

    Directory of Open Access Journals (Sweden)

    L. SOUZA

    Full Text Available Abstract Alkali-aggregate reaction is a chemical reaction between cement alkalis and some reactive mineral present in some aggregates, leading to concrete expansion and cracking. One kind usually observed and studied in Brazil is the alkali-silica reaction, due to its fast development. There are several methods that are effective to control and mitigate this reaction, and one of them is the partial replacement of cement by mineral additions such as pozzolans like fly-ash, silica fume and slag. In this study, we propose the use of electrical steel slag as a partial replacement of cement, evaluating its effectiveness by NBR 15577:2008, employing different proportions as replacement. It seems that the electrical steel slag, despite its expansive behavior, has been effective in the control of the ASR.

  8. Alkali silica reaction in concrete induced by mortar adhered to recycled aggregate

    Directory of Open Access Journals (Sweden)

    Etxeberria, M.


    Full Text Available The durability of recycled concrete must be determined before this material can be used in construction. In this paper the alkali-silica reaction in recycled concrete is analyzed. The recycled concrete is made with recycled aggregates, composed by original limestone aggregates and adhered mortar with reactive silica sand, and high alkali content cement. Due to the manufacturing process used for concrete production and the high water absorption capacity of recycled aggregates, cement accumulation happens in the interface (ITZ. The concentration of alkalis on the surface of recycled aggregates- ITZ and the presence of reactive sand in the mortar adhering to the recycled aggregate induce an alkali-silica reaction in 6-month concrete. The existence of this reaction is confirmed by environmental scanning electron microscopy (ESEM and EDX analysis. The mechanical properties of 6-month recycled concrete were similar to those values at 28-days of curing.

    La durabilidad del hormigón fabricado con árido reciclado es necesario determinarla antes de su utilización como material de construcción. En este artículo se analiza la reacción álcali-sílice manifestada en el hormigón fabricado con árido reciclado procedente de hormigón (compuesto de árido original calizo y mortero adherido de arena sílice reactiva, y cemento de alto contenido en álcalis. Debido al proceso de fabricación del hormigón y la alta capacidad de absorción del árido reciclado se produce una acumulación del cemento en la Interfase (ITZ. Debido al contacto directo de los álcalis del cemento con la arena sílice reactiva se produce una reacción álcali sílice a los 6 meses de edad del hormigón. Se realiza un análisis mediante microscopio electrónico de barrido ambiental (ESEM y sistema analítico de EDX. Se determina que las propiedades mecánicas del hormigón reciclado a 6 meses son similares a las obtenidas a los 28 días de curado.

  9. A plug flow model for chemical reactions and aerosol nucleation and growth in an alkali-containing flue gas

    DEFF Research Database (Denmark)

    Christensen, K. A.; Livbjerg, Hans


    multicomponent growth models are treated. The local gas phase composition is determined from a gas phase chemical equilibrium calculation combined with finite reaction rate kinetics for slower reactions. The model is useful in the analysis of boiler operation with respect to the formation of particles, HCl, SO2......The paper presents a numerical model for the simulation of gas to particle conversion and the chemical changes during cooling of a flue gas from the combustion of fuels rich in volatile alkali species. For the homogeneous nucleation of alkali species the model uses the classical theory modified...

  10. Carbon fibre-reinforced, alkali-activated slag mortars

    Directory of Open Access Journals (Sweden)

    Garcés, P.


    Full Text Available The paper describes the effect of carbon fibre on alkaliactivated slag mortar (AAS mechanical strength, volume stability and reinforcing steel corrosion, compared to its effect on the same properties in Portland cement (PC properties. Mechanical strength and volume stability tests were performed as set out in the respective Spanish UNE standards. The corrosion rate of steel embedded in the specimens studied was determined from polarization resistance analysis. One of the findings of the study performed was that carbon fibre failed to improve AAS or CP mortar strength. As far as volume stability is concerned, the inclusion of carbon fibres in AAS with a liquid/solid ratio of 0.5 reduced drying shrinkage by about 50%. The effect of carbon fibre on PC mortars differed from its effect on AAS mortars. Studies showed that in the presence of carbonation, steel corrosion reached higher levels in carbon-fibre reinforced AAS mortars; the inclusion of 1% carbon fibre improved corrosion resistance perceptibly in these same mortars, however, when exposed to chloride attack.Se ha estudiado el efecto de la incorporación de fibras de carbón en el comportamiento mecánico, estabilidad de volumen y nivel de corrosión de la armadura en morteros de escorias activadas alcalinamente (AAS. Se evalúa la influencia de las fibras de carbón en el comportamiento de morteros alcalinos en comparación con el efecto que producen en morteros de Portland (CP. Los ensayos mecánicos y de estabilidad de volumen se han realizado según lo establecido en la norma UNE que los regula. Se ha utilizado la técnica de la Resistencia a la Polarización para determinar la velocidad de corrosión del acero embebido en las muestras estudiadas. Como consecuencia del estudio realizado, se ha podido concluir que la adición de fibras de carbón a morteros de AAS y CP no mejora las características resistentes de los mismos. En relación con la estabilidad de volumen, la incorporación de

  11. Carbonation Characteristics of Alkali-Activated Blast-Furnace Slag Mortar

    Directory of Open Access Journals (Sweden)

    Keum-Il Song


    Full Text Available Alkali-activated ground granulated blast-slag (AAS is the most obvious alternative material for ordinary Portland cement (OPC. However, to use it as a structural material requires the assessment and verification of its durability. The most important factor for a durability evaluation is the degree of carbonation resistance, and AAS is known to show lower performance than OPC. A series of experiments was conducted with a view to investigate the carbonation characteristics of AAS binder. As a consequence, it was found that the major hydration product of AAS was calcium silicate hydrate (CSH, with almost no portlandite, unlike the products of OPC. After carbonation, the CSH of AAS turned into amorphous silica gel which was most likely why the compressive strength of AAS became weaker after carbonation. An increase of the activator dosage leads AAS to react more quickly and produce more CSH, increasing the compaction, compressive strength, and carbonation resistance of the microstructure.

  12. Microstructural Changes Due to Alkali-Silica Reaction during Standard Mortar Test

    Directory of Open Access Journals (Sweden)

    Jun-Ho Shin


    Full Text Available The microstructural development of mortar bars with silica glass aggregate undergoing alkali-silica reaction (ASR under the conditions of American Society for Testing and Materials (ASTM Standard Test C1260 was analyzed using scanning electron microscopy and qualitative X-ray microanalysis. Cracking in the aggregate, the hydrated paste, and the paste-aggregate interface was important in the development of the microstructure. Cracks were characterized according to their location, their relationship to other cracks, and whether they are filled with ASR gel. Expansion of the bars was approximately 1% at 12 days and 2% at 53 days. They fell apart by 63 days. The bars contained two zones, an inner region that was undergoing ASR and an outer and much more highly damaged zone that extended further inward over time. Evidence of ASR was present even during the period when specimens were immersed in water, prior to immersion in NaOH solution.

  13. Insights into alkali-silica reaction damage in mortar through acoustic nonlinearity (United States)

    Rashidi, M.; Kim, J.-Y.; Jacobs, L. J.; Kurtis, K. E.


    The progression of damage as a result of alkali-silica reaction in mortar samples is monitored by using the Nonlinear Impact Resonance Acoustic Spectroscopy (NIRAS) method and expansion measurements, which were performed daily. Results of this study show a strong correlation between the cumulative average nonlinearity parameter and expansion for each sample type, and a strong linear relationship between fourteen-day expansion and the cumulative average nonlinearity of among sample types. In addition to the cumulative average nonlinearity parameter, the standard deviation of average nonlinearity parameter shows strong correlation with the fourteen-day expansion of sample types. Results provide insights to the relationship with the acoustic nonlinearity and damage caused by the ASR.

  14. Influence of mesostasis in volcanic rocks on the alkali-aggregate reaction

    KAUST Repository

    Tiecher, Francieli


    Mesostasis material present in the interstices of volcanic rocks is the main cause of the alkali-aggregate reaction (AAR) in concretes made with these rock aggregates. Mesostasis often is referred to as volcanic glass, because it has amorphous features when analyzed by optical microscopy. However, this study demonstrates that mesostasis in the interstitials of volcanic rocks most often consists of micro to cryptocrystalline mineral phases of quartz, feldspars, and clays. Mesostasis has been identified as having different characteristics, and, thus, this new characterization calls for a re-evaluation of their influence on the reactivity of the volcanic rocks. The main purpose of this study is to correlate the characteristics of mesostasis with the AAR in mortar bars containing basalts and rhyolites. © 2012 Elsevier Ltd. All rights reserved.

  15. Microwave material characterization of alkali-silica reaction (ASR) gel in cementitious materials (United States)

    Hashemi, Ashkan

    Since alkali-silica reaction (ASR) was recognized as a durability challenge in cement-based materials over 70 years ago, numerous methods have been utilized to prevent, detect, and mitigate this issue. However, quantifying the amount of produced ASR byproducts (i.e., ASR gel) in-service is still of great interest in the infrastructure industry. The overarching objective of this dissertation is to bring a new understanding to the fundamentals of ASR formation from a microwave dielectric property characterization point-of-view, and more importantly, to investigate the potential for devising a microwave nondestructive testing approach for ASR gel detection and evaluation. To this end, a comprehensive dielectric mixing model was developed with the potential for predicting the effective dielectric constant of mortar samples with and without the presence of ASR gel. To provide pertinent inputs to the model, critical factors on the influence of ASR gel formation on dielectric and reflection properties of several mortar samples were investigated at R, S, and X-band. Effects of humidity, alkali content, and long-term curing conditions on ASR-prone mortars were also investigated. Additionally, dielectric properties of chemically different synthetic ASR gel were also determined. All of these, collectively, served as critical inputs to the mixing model. The resulting developed dielectric mixing model has the potential to be further utilized to quantify the amount of produced ASR gel in cement-based materials. This methodology, once becomes more mature, will bring new insight to the ASR reaction, allowing for advancements in design, detection and mitigation of ASR, and eventually has the potential to become a method-of-choice for in-situ infrastructure health-monitoring of existing structures.

  16. Modeling of alkali-silica reaction in concrete:a review

    Institute of Scientific and Technical Information of China (English)



    This paper presents a comprehensive review of modeling of alkali-silica reaction (ASR) in concrete.Such modeling is essential for investigating the chemical expansion mechanism and the subsequent influence on the mechanical aspects of the material.The concept of ASR and the mechanism of expansion are first outlined,and the stateof-the-art of modeling for ASR,the focus of the paper,is then presented in detail.The modeling includes theoretical approaches,meso-and macroscopic models for ASR analysis.The theoretical approaches dealt with the chemical reaction mechanism and were used for predicting pessimum size of aggregate.Mesoscopic models have attempted to explain the mechanism of mechanical deterioration of ASR-affected concrete at material scale.The macroscopic models,chemomechanical coupling models,have been generally developed by combining the chemical reaction kinetics with linear or nonlinear mechanical constitutive,and were applied to reproduce and predict the long-term behavior of structures suffering from ASR.Finally,a conclusion and discussion of the modeling are given.

  17. Interactions of alkali metals and electrolyte with cathode carbons

    Energy Technology Data Exchange (ETDEWEB)

    Naas, Tyke


    The Hall-Heroult process for electrolytic reduction of alumina has been the only commercial process for production of primary aluminium. The process runs at high temperature and it is important to minimize the energy consumption. To save energy it is desirable to reduce the operating temperature. This can be achieved by adding suitable additives such as LiF or KF to the cryolitic electrolyte. This may conflict with the objective of extending the lifetime of the cathode linings of the cell as much as possible. The thesis investigates this possibility and the nature of the interactions involved. It supports the hypothesis that LiF-additions to the Hall-Heroult cell electrolyte is beneficial to the carbon cathode performance because the diminished sodium activity reduces the sodium induced stresses during the initial period of electrolysis. The use of KF as an additive is more dangerous, but the results indicate that additions up to 5% KF may be tolerated in acidic melts with semigraphitic or graphitic cathodes with little risk of cathode problems. 153 refs., 94 figs., 30 tabs.

  18. Simultaneous Synthesis of Dimethyl Carbonate and Poly(ethylene terephthalate) Using Alkali Metals as Catalysts%碱金属化合物催化同时合成碳酸二甲酯和聚对苯二甲酸乙二醇酯

    Institute of Scientific and Technical Information of China (English)

    张丹; 王庆印; 姚洁; 王越; 曾毅; 王公应


    Dimethyl carbonate (DMC) and poly(ethylene terephthalate) was simultaneously synthesized by the transesterification of ethylene carbonate (EC) with dimethyl terephthalate (DMT) in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carried out under the following conditions: the reaction temperature 250℃, molar ratio of EC to DMT 3: 1, reaction time 3h, and catalyst amount 0.004 (molar ratio to DMT), the yield of DMC was 68.9%.

  19. Cascade enzymatic reactions for efficient carbon sequestration. (United States)

    Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping


    Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA.

  20. Monitoring, Modeling, and Diagnosis of Alkali-Silica Reaction in Small Concrete Samples

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Vivek [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cai, Guowei [Idaho National Lab. (INL), Idaho Falls, ID (United States); Gribok, Andrei V. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mahadevan, Sankaran [Idaho National Lab. (INL), Idaho Falls, ID (United States)


    Assessment and management of aging concrete structures in nuclear power plants require a more systematic approach than simple reliance on existing code margins of safety. Structural health monitoring of concrete structures aims to understand the current health condition of a structure based on heterogeneous measurements to produce high-confidence actionable information regarding structural integrity that supports operational and maintenance decisions. This report describes alkali-silica reaction (ASR) degradation mechanisms and factors influencing the ASR. A fully coupled thermo-hydro-mechanical-chemical model developed by Saouma and Perotti by taking into consideration the effects of stress on the reaction kinetics and anisotropic volumetric expansion is presented in this report. This model is implemented in the GRIZZLY code based on the Multiphysics Object Oriented Simulation Environment. The implemented model in the GRIZZLY code is randomly used to initiate ASR in a 2D and 3D lattice to study the percolation aspects of concrete. The percolation aspects help determine the transport properties of the material and therefore the durability and service life of concrete. This report summarizes the effort to develop small-size concrete samples with embedded glass to mimic ASR. The concrete samples were treated in water and sodium hydroxide solution at elevated temperature to study how ingress of sodium ions and hydroxide ions at elevated temperature impacts concrete samples embedded with glass. Thermal camera was used to monitor the changes in the concrete sample and results are summarized.

  1. Classification of alkali-silica reaction and corrosion distress using acoustic emission (United States)

    Abdelrahman, Marwa; ElBatanouny, Mohamed; Serrato, Michael; Dixon, Kenneth; Larosche, Carl; Ziehl, Paul


    The Nuclear Regulatory Commission regulates approximately 100 commercial nuclear power reactor facilities that contribute about 20% of the total electric energy produced in the United States. Half of these reactor facilities are over 30 years old and are approaching their original design service life. Due to economic and durability considerations, significant portions of many of the facilities were constructed with reinforced concrete, including the containment facilities, cooling towers, and foundations. While most of these concrete facilities have performed exceptionally well throughout their initial expected service life, some are beginning to exhibit different forms of concrete deterioration. In this study, acoustic emission (AE) is used to monitor two main concrete deterioration mechanisms; alkali-silica reaction (ASR) distress and corrosion of reinforcing steel. An accelerated ASR test was conducted where specimens were continuously monitored with AE. The results show that AE can detect and classify damage due to ASR distress in the specimens. AE was also used to remotely monitor active corrosion regions in a reactor facility. AE monitoring of accelerated corrosion testing was also conducted on a concrete block specimen cut from a similar reactor building. Electrochemical measurements were conducted to correlate AE activity to quantifiable corrosion measurements and to enhance capabilities for service life prediction.

  2. Use of Fly Ash in the Mitigation of Alkali-Silica Reaction in Concrete (United States)


    crystallinity of the silica and its solubility. Common reactive minerals susceptible to ASR include strained quartz, cristobalite , opal, obsidian, chert, and...residues, whereas alkali-silica reactive components include opal, cristobalite , tridymite, siliceous and some intermediate volcanic glass, chert

  3. The Influence of Calcined Clay Pozzolan, Low-Cao Steel Slag and Granite Dust On the Alkali-Silica Reaction in Concrete


    James Sarfo-Ansah; Eugene Atiemo


    The influence of low CaO steel slag, calcined clay and granite dust on the alkali-silica reaction was investigated over a period of 35 days under accelerated curing conditions. The mineral admixtures were used to replace varying portions of high alkali Portland limestone cement up to an admixture content of 25% in order to study their effect on the alkali-silica reaction (ASR). Portland limestone cement used for the study had a total Na2Oeq of 4.32. XRD analysis of hydrated mortar...

  4. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin


    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Quantitative diagnosis and prognosis framework for concrete degradation due to alkali-silica reaction (United States)

    Mahadevan, Sankaran; Neal, Kyle; Nath, Paromita; Bao, Yanqing; Cai, Guowei; Orme, Peter; Adams, Douglas; Agarwal, Vivek


    This research is seeking to develop a probabilistic framework for health diagnosis and prognosis of aging concrete structures in nuclear power plants that are subjected to physical, chemical, environment, and mechanical degradation. The proposed framework consists of four elements: monitoring, data analytics, uncertainty quantification, and prognosis. The current work focuses on degradation caused by ASR (alkali-silica reaction). Controlled concrete specimens with reactive aggregate are prepared to develop accelerated ASR degradation. Different monitoring techniques — infrared thermography, digital image correlation (DIC), mechanical deformation measurements, nonlinear impact resonance acoustic spectroscopy (NIRAS), and vibro-acoustic modulation (VAM) — are studied for ASR diagnosis of the specimens. Both DIC and mechanical measurements record the specimen deformation caused by ASR gel expansion. Thermography is used to compare the thermal response of pristine and damaged concrete specimens and generate a 2-D map of the damage (i.e., ASR gel and cracked area), thus facilitating localization and quantification of damage. NIRAS and VAM are two separate vibration-based techniques that detect nonlinear changes in dynamic properties caused by the damage. The diagnosis results from multiple techniques are then fused using a Bayesian network, which also helps to quantify the uncertainty in the diagnosis. Prognosis of ASR degradation is then performed based on the current state of degradation obtained from diagnosis, by using a coupled thermo-hydro-mechanical-chemical (THMC) model for ASR degradation. This comprehensive approach of monitoring, data analytics, and uncertainty-quantified diagnosis and prognosis will facilitate the development of a quantitative, risk informed framework that will support continuous assessment and risk management of structural health and performance.

  6. Alkali metal cation doped Al-SBA-15 for carbon dioxide adsorption. (United States)

    Zukal, Arnošt; Mayerová, Jana; Čejka, Jiří


    Mesoporous aluminosilicate adsorbents for carbon dioxide were prepared by the grafting of aluminium into SBA-15 silica using an aqueous solution of aluminium chlorohydrate. As the ion exchange sites are primarily associated with the presence of tetrahedrally coordinated aluminium, extra-framework aluminium on the SBA-15 surface was inserted into the silica matrix by a treatment with an aqueous solution of NH(4)OH. Synthesized mesoporous aluminosilicate preserving all the characteristic features of a mesoporous molecular sieve was finally modified by the alkali metal cation exchange. To examine carbon dioxide adsorption on prepared materials, adsorption isotherms in the temperature range from 0 °C to 60 °C were measured. Based on the known temperature dependence of adsorption isotherms, isosteric adsorption heats giving information on the surface energetics of CO(2) adsorption were calculated and discussed. The comparison of carbon dioxide isotherms obtained on aluminosilicate SBA-15, aluminosilicate SBA-15 containing cations Na(+) and K(+) and activated alumina F-200 reveals that the doping with sodium or potassium cations dramatically enhances adsorption in the region of equilibrium pressures lower than 10 kPa. Therefore, synthesized aluminosilicate adsorbents doped with Na(+) or K(+) cations are suitable for carbon dioxide separation from dilute gas mixtures.

  7. Effect of Glass Powder on Chloride Ion Transport and Alkali-aggregate Reaction Expansion of Lightweight Aggregate Concrete

    Institute of Scientific and Technical Information of China (English)

    WANG Zhi; SHI Caijun; SONG Jianming


    The effects of glass powder on the strength development, chloride permeability and potential alkali-aggregate reaction expansion of lightweight aggregate concrete were investigated.Ground blast furnace slag, coal fly ash and silica fume were used as reference materials. The re-placement of cement with 25% glass powder slightly decreases the strengthes at 7 and 28 d, but shows no effect on 90 d's. Silica fume is very effective in improving both the strength and chloride penetra-tion resistance, while ground glass powder is much more effective than blast furnace slag and fly ash in improving chloride penetration resistance of the concrete. When expanded shale or clay is used as coarse aggregate, the concrete containing glass powder does not exhibit deleterious expansion even if alkali-reactive sand is used as fine aggregate of the concrete.

  8. Expansion of powerhouse structures due to alkali-aggregate reaction and the use of low calcium fly ash to ameliorate the reaction in future construction

    Energy Technology Data Exchange (ETDEWEB)

    Langley, W.S. [W.S. Langley Concrete and Material Technology Inc., NS (Canada); Brown, E. [Nova Scotia Power Corp., Halifax, NS (Canada)


    A study was conducted to examine a reaction in concrete between the alkalies found in the pore fluid and certain siliceous aggregates. This reaction, called alkali-aggregate reactivity caused disruptive expansion in a concrete powerhouse structure in Nova Scotia in 1962. The structure was constructed with meta-sediments and biotite schists. This combination caused expansion and resulted in problems with the operation of the plant within 10 years after construction. Subsequent studies showed that the reactive aggregates were widespread and that the problem could be solved using 15 to 30 per cent fly ash replacement of the cement. Now, low calcium fly ash is used on a regular basis to lessen the potential for alkali-aggregate reaction. Nova Scotia fly ash was also being studied for its use as a cement replacement and enhancement of concrete durability. It was concluded that this particular fly ash is an excellent supplementary cement material to offset disruptive expansions. The fly ash has been used since the mid 1980s for solving expansion problems in powerhouses. 6 refs., 3 tabs., 12 figs.

  9. Influence of alkali, silicate, and sulfate content of carbonated concrete pore solution on mild steel corrosion behavior

    Energy Technology Data Exchange (ETDEWEB)

    L' Hostis, V. [CEA Saclay, DEN, DPC, SCCME, Lab Etud Comportement Betons and Argiles, F-91191 Gif Sur Yvette (France); Huet, B. [Schlumberger Riboud Prod Ctr, Schlumberger Carbon Serv, F-92142 Clamart (France); Tricheux, L. [CEBTP SOLEN, F-78990 Elancourt (France); Idrissi, H. [CNRS, Lab MATEIS UMR 5510, Equipe RI2S, Dept Sci and Genie Mat, F-69621 Villeurbanne (France)


    The increase in the rebar corrosion rate due to the concrete carbonation is the major cause of reinforced concrete degradation. The aim of this study was to investigate the corrosion behavior of mild steel rebars in simulated carbonated concrete solution. For this purpose, thermodynamic calculations, electrochemical techniques, gravimetric measurements, and surface analyses were used. Thermodynamic investigations of the nature of the interstitial solution provides an estimation of the influence of sulfate (SO{sub 4}{sup 2-}) and alkali (Na{sup +}, K{sup +}) content on carbonate alkalinity of the CO{sub 2}/H{sub 2}O open system (pCO{sub 2}=0. 3 mbar). in this system, calcium-silicate hydrates (C-S-H) remain thermodynamically unstable and amorphous silica controls silicate aqueous content at 100 ppm. Electrochemical results highlight a decrease in the corrosion rate with increasing carbonate alkalinity and the introduction of silicate. The introduction of sulfate at fixed carbonate alkalinity shows a dual effect: at high carbonate alkalinity, the corrosion rate is increased whereas at low carbonate alkalinity, corrosion rate is decreased. Those results are supported by surface analysis. Authors conclude that silicate and sulfate release from cement hydrates and fixation of alkali on carbonated hydrates are key parameters to estimate mild steel corrosion in carbonated concrete. (authors)

  10. Influence of alkali, silicate, and sulfate content of carbonated concrete pore solution on mild steel corrosion behavior

    Energy Technology Data Exchange (ETDEWEB)

    Huet, B. [Schlumberger Carbon Services, Schlumberger Riboud Product Center, Clamart (France); L' Hostis, V. [CEA, DEN, DPC, SCCME, Laboratoire d' Etude du Comportement des Betons et des Argiles, Gif-sur-Yvette, (France); Tricheux, L. [CEBTP-SOLEN, Elancourt, (France); Idrissi, H. [Laboratoire MATEIS UMR CNRS, Equipe RI2S, Department Science et Genie des Materiaux, Villeurbanne, (France)


    The increase in the rebar corrosion rate due to the concrete carbonation is the major cause of reinforced concrete degradation. The aim of this study was to investigate the corrosion behavior of mild steel rebars in simulated carbonated concrete solution. For this purpose, thermodynamic calculations, electrochemical techniques, gravimetric measurements, and surface analyses were used. Thermodynamic investigations of the nature of the interstitial solution provides an estimation of the influence of sulfate (SO{sub 4}{sup 2} {sup -}) and alkali (Na{sup +}, K{sup +}) content on carbonate alkalinity of the CO{sub 2}/H{sub 2}O open system (pCO{sub 2} = 0.3 mbar). In this system, calcium-silicate hydrates (C-S-H) remain thermodynamically unstable and amorphous silica controls silicate aqueous content at 100 ppm. Electrochemical results highlight a decrease in the corrosion rate with increasing carbonate alkalinity and the introduction of silicate. The introduction of sulfate at fixed carbonate alkalinity shows a dual effect: at high carbonate alkalinity, the corrosion rate is increased whereas at low carbonate alkalinity, corrosion rate is decreased. Those results are supported by surface analysis. Authors conclude that silicate and sulfate release from cement hydrates and fixation of alkali on carbonated hydrates are key parameters to estimate mild steel corrosion in carbonated concrete. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  11. Chemical reactions confined within carbon nanotubes. (United States)

    Miners, Scott A; Rance, Graham A; Khlobystov, Andrei N


    In this critical review, we survey the wide range of chemical reactions that have been confined within carbon nanotubes, particularly emphasising how the pairwise interactions between the catalysts, reactants, transition states and products of a particular molecular transformation with the host nanotube can be used to control the yields and distributions of products of chemical reactions. We demonstrate that nanoscale confinement within carbon nanotubes enables the control of catalyst activity, morphology and stability, influences the local concentration of reactants and products thus affecting equilibria, rates and selectivity, pre-arranges the reactants for desired reactions and alters the relative stability of isomeric products. We critically evaluate the relative advantages and disadvantages of the confinement of chemical reactions inside carbon nanotubes from a chemical perspective and describe how further developments in the controlled synthesis of carbon nanotubes and the incorporation of multifunctionality are essential for the development of this ever-expanding field, ultimately leading to the effective control of the pathways of chemical reactions through the rational design of multi-functional carbon nanoreactors.

  12. Reactions on carbon anodes in aluminium electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Eidet, Trygve


    The consumption of carbon anodes and energy in aluminium electrolysis is higher than what is required theoretically. This thesis studies the most important of the reactions that consume anode materials. These reactions are the electrochemical anode reaction and the airburn and carboxy reactions. The first part of the thesis deals with the kinetics and mechanism of the electrochemical anode reaction using electrochemical impedance spectroscopy. The second part deals with air and carboxy reactivity of carbon anodes and studies the effects of inorganic impurities on the reactivity of carbon anodes in the aluminium industry. Special attention is given to sulphur since its effect on the carbon gasification is not well understood. Sulphur is always present in anodes, and it is expected that the sulphur content of available anode cokes will increase in the future. It has also been suggested that sulphur poisons catalyzing impurities in the anodes. Other impurities that were investigated are iron, nickel and vanadium, which are common impurities in anodes which have been reported to catalyze carbon gasification. 88 refs., 92 figs., 24 tabs.

  13. Modelling The Effects of Aggregate Size on Alkali Aggregate Reaction Expansion

    Directory of Open Access Journals (Sweden)

    N. Z. Sekrane


    Full Text Available This work aims at developing models to predict the potential expansion of concrete containing alkali-reactive aggregates. The paper gives measurements in order to provide experimental data concerning the effect of particle size of an alkali-reactive siliceous limestone on mortar expansion. Results show that no expansion was measured on the mortars using small particles (0.5-1.0 mm while the particles (1.0–2.0 mm gave the largest expansions (0.217%. Two models are proposed, the first one studies the correlations between the measured expansions and the size of aggregates, the second one calculates the thickness of the porous zone necessary to take again all the volume of the gel created.

  14. Reaction of chromalumozirconium refractory with alkali-free borosilicate glass melt

    Energy Technology Data Exchange (ETDEWEB)

    Popov, O.N.; Frolova, V.P.


    The corrosion mechanism of chromalumozirconium refractory synthesized on the base of the Cr/sub 2/O/sub 3/-Al/sub 2/O/sub 3/-ZrO/sub 2/-SiO/sub 2/ system by the alkali-free borosilicate ''E'' glass melt is investigated. It is estalished that in the process of refractory destruction the diffusion zonality is formed in it being a reflection of comparative migration activity of refractory components.

  15. Selectivity in the carbon-oxygen reaction (United States)

    Skokova, Kristina A.

    The dependence of the carbon-oxygen reaction rate and the CO/COsb2 ratio on temperature, oxygen pressure, carbon crystallite size, concentration of surface C(O) complexes, and content of heteroatoms was studied. It was shown that the temperature dependence of the CO/COsb2 ratio obeys an Arrhenius-type relationship, but the pre-exponential factor and the activation energy depend on oxygen pressure and carbon nature. The Arrhenius parameters were found to be directly proportional to each other. This confirmed the importance of the compensation effect in carbon oxidation. It was explained by active site heterogeneity in carbon materials. For all experimental conditions, the CO/COsb2 ratio was lower for carbons with more ordered graphitic structure. It was shown that the CO/COsb2 ratio is inversely proportional to the surface coverage with reactive C(O) complexes. More ordered carbons were revealed to possess lower concentrations of stable complexes, higher surface coverages with reactive complexes and thus lower CO/COsb2 ratios. The influence of B and N heteroatoms on carbon reactivity and the CO/COsb2 ratio was studied. It was confirmed that B acts as an inhibitor of carbon oxidation due to the formation of a protective Bsb2Osb3 coating. The N presence in the carbon structure increases its rate of oxidation, maybe due to decreasing carbon crystallite dimensions. The CO/COsb2 ratio did not correlate with the N content in the carbon, but depended on the concentration of surface carbon-oxygen complexes. A new reaction mechanism is proposed. A key feature of the mechanism is that it takes into account the presence and mobility of oxygen atoms on the basal plane. It was shown with the aid of theoretical molecular orbital calculations that chemisorption on a pair of adjacent edge and basal sites is thermodynamically favorable as a parallel process to the generally accepted path of chemisorption on two edge carbon atoms. The former process can lead to the formation of a

  16. Reactions of chromium-aluminum-zirconium refractory with a molten alkali-free borosilicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Popov, O.N.; Frolova, V.P.


    The authors consider the scope for using KhTs-45 refractory containing in mass % 45.0 Cr2O3, 5.0 Al2O3, 32.5 ZrO2, 16.0 SiO2, and 1.5 Na2O for melting alkali-free borosilicate glass E, and they also present some experimental results on the corrosion of the refractory in contact with the molten glass and on the contact mineral formation. They conclude that during the attack on the refractory diffusion zoning is formed, which reflects the relative component migration activities.

  17. Diffusion with chemical reaction: An attempt to explain number density anomalies in experiments involving alkali vapor (United States)

    Snow, W. L.


    The mutual diffusion of two reacting gases is examined which takes place in a bath of inert gas atoms. Solutions are obtained between concentric spheres, each sphere acting as a source for one of the reactants. The calculational model is used to illustrate severe number density gradients observed in absorption experiments with alkali vapor. Severe gradients result when sq root k/D R is approximately 5 where k, D, and R are respectively the second order rate constant, the multicomponent diffusion constant, and the geometrical dimension of the experiment.

  18. Methods for Controlling Effects of Alkali-Silica Reaction in Concrete. (United States)


    and high-alkali RC-756(2) cements were used. The reactive aggregates were opal, glassy igneous rock, and chert produced by crushing chert gravel. As...tridymite High- and low-temperature Minor cristobalite I i %’I There was probably also some amorphous material. Similar work with a separate hand sample...CONIP STESNOTE. 0. psi WALSE SET-0EN Pd U AUTOCLAVE SRP..%U-O INITAL 5*N/I INAL SET. NO/- :4( AUTOCLAVE SEP.. % INTIAL. SET. NOR/-S FINAL. SGT

  19. Field emission properties of capped carbon nanotubes doped by alkali metals:a theoretical investigation

    Institute of Scientific and Technical Information of China (English)

    Jin Lei; Fu Hong-Gang; Xie Ying; Yu Hai-Tao


    The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.

  20. Dispersion C3 coefficients for the alkali-metal atoms interacting with a graphene layer and with a carbon nanotube

    CERN Document Server

    Arora, Bindiya; Sahoo, B K


    We evaluate separation dependent van der Waal dispersion ($C_3$) coefficients for the interactions of the Li, Na, K and Rb alkali atoms with a graphene layer and with a single walled carbon nanotube (CNT) using the hydrodynamic and Dirac models. The results from both the models are evaluated using accurate values of the dynamic polarizabilities of the above atoms. Accountability of these accurate values of dynamical polarizabilities of the alkali atoms in determination of the above $C_3$ coefficients are accentuated by comparing them with the coefficients evaluated using the dynamic dipole polarizabilities estimated from the single oscillator approximation which are typically employed in the earlier calculations. For practical description of the atom-surface interaction potentials the radial dependent $C_3$ coefficients are given for a wide range of separation distances between the ground states of the considered atoms and the wall surfaces and also for different values of nanotube radii. The coefficients for...

  1. Promoting Effect of Inorganic Alkali on Carbon Dioxide Adsorption in Amine-Modified MCM-41

    Directory of Open Access Journals (Sweden)

    Yang Teng


    Full Text Available Three kinds of inorganic alkali are introduced into tetraethylenepentamine (TEPA and polyethyleneimine (PEI-modified MCM-41 as the CO2 adsorbents. X-ray diffraction, N2 adsorption, fourier-transform infrared and thermo gravimetric analysis are used to characterize the surface structures and the thermal stability of adsorbents. Chemical titration method is used to measure the alkali amounts of adsorbents. Thermo-gravimetric analysis with 10% CO2/90% N2 as the simulated flue gas is used to test the CO2 adsorption performance of adsorbents. The results show that all three kinds of inorganic alkali-containing adsorbents exhibit higher CO2 adsorption capability than traditional TEPA and PEI modified samples. Ca(OH2 and PEI modified samples exhibit the highest adsorption capacity and recyclable property. The introduction of inorganic alkali changes the chemical adsorption mechanism between CO2 and adsorbent surface due to the increased hydroxyl groups. The CO2 adsorption capacities have a linear dependence relation with the alkali amounts of adsorbents, indicating that alkali amount is a critical factor for the exploration of novel adsorbents.

  2. Tuning indium tin oxide work function with solution-processed alkali carbonate interfacial layers for high-efficiency inverted organic photovoltaic cells. (United States)

    Chen, Fei; Chen, Qi; Mao, Lin; Wang, Yixin; Huang, Xun; Lu, Wei; Wang, Bing; Chen, Liwei


    Selective electron collection by an interfacial layer modified indium tin oxide cathode is critically important for achieving high-efficiency inverted structure organic photovoltaic (OPV) cells. Here, we demonstrate that solution-processed alkali carbonates, such as Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, are good interfacial layer materials. Both carbonate concentration and annealing conditions can affect cathode work function and surface roughness. By proper optimization, different alkali carbonates can be almost equally effective as the cathode interfacial layer. Furthermore, good device performance can be achieved at a low annealing temperature (cells on plastic substrates. This work indicates that alkali carbonates, not just cesium carbonate, are valid choices as the cathode interlayer in inverted OPV devices.

  3. Effect of charge density in chain extension reactions involving complexes of 4, 4'-diaminodiphenylmethane and various alkali metal salts (United States)

    Deshmukh, Subrajeet; Carrasquillo, Katherine; Tsai, Fang Chang; Wu, Lina; Hsu, Shaw Ling; University of Massachusetts Amherst Team

    Controlling the reaction of methylene diphenyl diisocyanate (MDI)-terminated polyester prepolymer and 4, 4'-diaminodiphenylmethane (MDA) is extremely important in many large scale applications. The ion-diamine complex has the advantage of blocking the instantaneous reaction between the diamine and isocyanate from taking place until it is released at elevated temperatures. We synthesized complexes of MDA with various alkali metal salts. These complexes create a barrier between the diamine and isocyanate thus preventing the premature reaction. We compared the complexes in terms of their dissociation and the subsequent curing with the prepolymer. Charge density had a tremendous effect. DSC showed that Na complexes dissociated at a lower temperature and needed less energy to dissociate than the Li complexes. The effect of change in cation on complex dissociation was more pronounced compared to the change in anion. Also, the ionic liquid introduced greatly altered the dissociation behavior. Temperature and time resolved IR spectroscopy was used to monitor the urea and NH band. By DSC and IR, we showed that NaCl complex is best suited for the curing of prepolymer with regards to curing temperature and energy.

  4. Some Organic Reactions in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    JIANG Huan-feng; YANG Xiao-yue; LI Guo-ping; ZOU Gang


    Organic reactions in supercritical carbon dioxide (scCO2) have facilitated great progress in recent years 1. ScCO2, as an environmentally friendly reaction medium, may be a substitute for volatile and toxic organic solvents and show some special advantages. Firstly, CO2 is inexpensive,nonflammable, nontoxic and chemical inert under many conditions. Secondly, scCO2 possesses hybrid properties of both liquid and gas, to the advantage of some reactions involving gaseous reagents. Control of the solvent density by variation of the temperature and pressure enables the solvent properties to be "tuned" to reactants. Finally, separating of CO2 from the reaction mixture is energy-efficient and simple. Here we disclose our new work on some organic reactions involving small molecules in scCO2.The results showed that the upper reactions in scCO2 could be carried out smoothly and thepressure of CO2 had a remarkable effect on the conversion and selectivity.

  5. Urea hydrolysis and calcium carbonate reaction fronts (United States)

    Fox, D. T.; Redden, G. D.; Henriksen, J.; Fujita, Y.; Guo, L.; Huang, H.


    The mobility of toxic or radioactive metal contaminants in subsurface environments can be reduced by the formation of mineral precipitates that form co-precipitates with the contaminants or that isolate them from the mobile fluid phase. An engineering challenge is to control the spatial distribution of precipitation reactions with respect to: 1) the location of a contaminant, and 2) where reactants are introduced into the subsurface. One strategy being explored for immobilizing contaminants, such as Sr-90, involves stimulating mineral precipitation by forming carbonate ions and hydroxide via the in situ, microbially mediated hydrolysis of urea. A series of column experiments have been conducted to explore how the construction or design of such an in situ reactant production strategy can affect the temporal and spatial distribution of calcium carbonate precipitation, and how the distribution is coupled to changes in permeability. The columns were constructed with silica gel as the porous media. An interval midway through the column contained an adsorbed urease enzyme in order to simulate a biologically active zone. A series of influent solutions were injected to characterize hydraulic properties of the column (e.g., bromide tracer), profiles of chemical conditions and reaction products as the enzyme catalyzes urea hydrolysis (e.g., pH, ammonia, urea), and changes that occur due to CaCO3 precipitation with the introduction of a calcium+urea solutions. In one experiment, hydraulic conductivity was reduced as precipitate accumulated in a layer within the column that had a higher fraction of fine grained silica gel. Subsequent reduction of permeability and flow (for a constant head condition) resulted in displacement of the hydrolysis and precipitation reaction profiles upstream. In another experiment, which lacked the physical heterogeneity (fine grained layer), the precipitation reaction did not result in loss of permeability or flow velocity and the reaction profile

  6. Alkali-silica reaction of aggregates for concrete pavements in Chihuahua’s State, Mexico

    Directory of Open Access Journals (Sweden)

    Olague, C.


    Full Text Available The concrete of pavements must resist the climatic conditions, heavy traffic, chemical agents or any other type of aggressive agent. A methodology for characterizing materials that would influence concrete durability was developed considering chemical and physical factors. This methodology allows the consideration of several factors like physiography, geology, and climate, among others that would be of great importance to prevent future durability problems of pavements. This methodology takes into account several tests and this paper presents the results of potential reactivity aggregates of the State of Chihuahua. The tests for evaluating the reactive siliceous aggregate and the potential alkali-silica reactivity were performed according to the: petrographic examination (ASTM C 295 and standard quick chemical test (ASTM C 289. 38% of the tested sites resulted innocuous, 48% potentially reactive and 13% reactive. It is discussed the benefit of applying a conscious methodology in order to obtain the best results with a representative quantity of tests.

    El hormigón de los pavimentos debe ser resistente a las condiciones climáticas, tránsito pesado, agentes químicos o cualquier otro tipo de agente agresivo. Se desarrolló una metodología para caracterización de materiales considerando factores físicos y químicos que influyen en la durabilidad del hormigón. Esta metodología se basa en la consideración de varios factores como: fisiografía, geología y clima, entre otros, que podrían ser de gran importancia para prevenir futuros problemas de durabilidad en pavimentos de hormigón. La metodología en cuestión considera varias pruebas, en este artículo se presentan los resultados de la reactividad potencial de los áridos del Estado de Chihuahua. Las pruebas para evaluar la reactividad de áridos silíceos y la reactividad potencial álcali-sílice fueron ejecutadas de acuerdo a: examen petrográfico (ASTM C 295 y la prueba qu

  7. Catalytic activity of carbons for methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922 (United States)


    Catalytic decomposition of methane is an environmentally attractive approach to CO{sub 2}-free production of hydrogen. The objective of this work is to evaluate catalytic activity of a wide range of carbon materials for methane decomposition reaction and determine major factors governing their activity. It was demonstrated that the catalytic activity of carbon materials for methane decomposition is mostly determined by their structural and surface properties. Kinetics of methane decomposition reaction over disordered (amorphous) carbons such as carbon black and activated carbon were determined. The mechanism of carbon-catalyzed methane decomposition reaction and the nature of active sites on the carbon surface are discussed in this paper.

  8. Thermochemical analysis of laterite ore alkali roasting: Comparison of sodium carbonate, sodium sulfate, and sodium hydroxide (United States)

    Samadhi, Tjokorde Walmiki


    The abundance of global nickel reserve is in fact dominated by low grade laterite ores containing only approximately 1.0-1.8 %-Ni. Indonesia is a major limonite and saprolite ores source, particularly in the Sulawesi, northern Maluku, and Papua islands. Production of nickel from laterites typically requires a pre-concentration step which breaks down the mineral crystalline structure, thereby facilitating the subsequent extraction of the valuable metals. This work discusses the thermochemical analysis of the alkali roasting of an Indonesian saprolite ore using Na2CO3, Na2SO4, and NaOH. These alkali compounds are selected due to their relatively low cost. The Factsage thermochemical computation package is used to predict thermodynamically stable gaseous, solution, pure liquid, and pure solid phases present in the roasting process at temperatures from 100 to 1200°C at ambient pressure, in inert atmosphere. The formation of a liquid solution (or slag) phase is interpreted as a major indicator of mineral structure breakdown. The computed slag formation temperatures are 373.2, 1041.4, and 792.0°C when using Na2CO3, Na2SO4, and NaOH, respectively. The masses of volatilized alkali at 1200°C with a total feed mass of 100 gram are 0.49, 3.24, and 3.25 mg for Na2CO3, Na2SO4, and NaOH, respectively. It is therefore hypothesized that Na2CO3 is the most competitive sodium-based alkali for saprolite ore roasting.

  9. Development of microwave and impedance spectroscopy methods for in-situ nondestructive evaluation of alkali silica reaction in concrete (United States)

    Heifetz, Alexander; Bakhtiari, Sasan; Lu, Juan; Aranson, Igor S.; Vinokur, Valerii M.; Bentivegna, Anthony F.


    Aging concrete degradation due to alkali silica reaction (ASR) is a challenge to sustainability of critical infrastructure, such as nuclear power plants. Currently, there is no standard, nondestructive method for detecting ASR in concrete. We report on the progress in developing electromagnetic (EM) methods, consisting of microwave and impedance spectroscopy techniques, for nondestructive detection of ASR. The microwave and impedance spectroscopy methods are complementary since they provide information about material electrical properties in GHz and Hz to KHz EM spectral bands, respectively. Preliminary studies were conducted using accelerated testing concrete prism specimens developed according to ASTM C1293 standard. Microwave and impedance spectroscopy measurements were performed on ASR specimens at the first and the second month maturity level, as well as on age-matched controls. Microwave tests consisted of reflection and transmission measurements using dielectric-loaded antennas, with the focus on X-band spectrum. Impedance measurements were performed using flexible electrode patches. Measurement results by both microwave and impedance spectroscopy methods indicate observable differences in electrical properties between reactive and non-reactive specimens. In addition, trends in measurement data obtained with the two complementary EM techniques are consistent and correlate with ASR progression in specimens.

  10. Alkali- or acid-induced changes in structure, moisture absorption ability and deacetylating reaction of β-chitin extracted from jumbo squid (Dosidicus gigas) pens. (United States)

    Jung, Jooyeoun; Zhao, Yanyun


    Alkali- or acid-induced structural modifications in β-chitin from squid (Dosidicus gigas, d'Orbigny, 1835) pens and their moisture absorption ability (MAA) and deacetylating reaction were investigated and compared with α-chitin from shrimp shells. β-Chitin was converted into the α-form after 3h in 40% NaOH or 1-3 h in 40% HCl solution, and α-chitin obtained from NaOH treatment had higher MAA than had native α-chitin, due to polymorphic destructions. In contrast, induced α-chitin from acid treatment of β-chitin had few polymorphic modifications, showing no significant change (P>0.05) in MAA. β-Chitin was more susceptible to alkali deacetylation than was α-chitin, and required a lower concentration of NaOH and shorter reaction time. These results demonstrate that alkali- or acid-treated β-chitin retained high susceptibility toward solvents, which in turn resulted in good biological activity of β-chitosan for use as a natural antioxidant and antimicrobial substance or application as edible coatings and films for various food applications.

  11. Fast ionic conduction in tetravalent metal pyrophosphate-alkali carbonate composites: New potential electrolytes for intermediate-temperature fuel cells (United States)

    Singh, Bhupendra; Bhardwaj, Aman; Gautam, Sandeep K.; Kumar, Devendra; Parkash, Om; Kim, In-Ho; Song, Sun-Ju


    Here we present a report on synthesis and characterization of tetravalent metal pyrophosphate (TMP) and alkali carbonate (A2CO3; A = Li and/or Na) composites. The TMP-carbonate composites are prepared by mixing indium-doped tin pyrophosphate or yttrium-doped zirconium pyrophosphate with Li2CO3 or an eutectic mixture of Li2CO3-Na2CO3 in different wt.% ratios. The phase composition, microstructure and electrical conductivity of the sintered specimen are analyzed. In addition, the effect of different TMP and A2CO3 phases is investigated. A maximum ionic conductivity of 5.5 × 10-2 S cm-1 at 630 °C is observed in this study with a Sn0.9In0.1P2O7-Li2CO3 composite. Based on the literature data, TMP-carbonate composites can be considered to be primarily a proton and oxygen-ion co-ionic conductor and, therefore, have strong potential as electrolytes in fuel cells in 500-700 °C range.

  12. The effect of carbon nanotubes on chiral chemical reactions (United States)

    Rance, Graham A.; Miners, Scott A.; Chamberlain, Thomas W.; Khlobystov, Andrei N.


    The intrinsic helicity of carbon nanotubes influences the formation of chiral molecules in chemical reactions. A racemic mixture of P and M enantiomers of nanotubes affects the enantiomeric excess of the products of the autocatalytic Soai reaction proportional to the amount of nanotubes added in the reaction mixture. An intermediate complex formed between the nanotube and the organometallic reagent is essential and explains the observed correlation between the enantiomeric distribution of products and the curvature of the carbon nanostructure. This Letter establishes a key mechanism for harnessing the helicity of nanoscale carbon surfaces for preparative organic reactions.

  13. Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

    Institute of Scientific and Technical Information of China (English)

    Yan Cao; Yunxia Zhao; Fujiao Song; Qin Zhong


    Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-1(also named Cu-BTC or MOF-199) was chemically reduced by doping it with alkali metals (Li, Na and K) and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction (XRD), thermo-gravimetric analysis (TGA) and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li+, Na+ and K+, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11%increase in adsorption capacity at 298 K and 18 bar as compared with HKUST-1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.

  14. Complex formation during dissolution of metal oxides in molten alkali carbonates

    DEFF Research Database (Denmark)

    Li, Qingfeng; Borup, Flemming; Petrushina, Irina;


    Dissolution of metal oxides in molten carbonates relates directly to the stability of materials for electrodes and construction of molten carbonate fuel cells. In the present work the solubilities of PbO, NiO, Fe2O3,and Bi2O3 in molten Li/K carbonates have been measured at 650 degrees C under...... carbon dioxide atmosphere. It is found that the solubilities of NiO and PbO decrease while those of Fe2O3 and Bi2O3 remain approximately constant as the lithium mole fraction increases from 0.43 to 0.62 in the melt. At a fixed composition of the melt, NiO and PbO display both acidic and basic dissolution...

  15. Demixing and effective volatility of molten alkali carbonate melts in MCFCs

    Energy Technology Data Exchange (ETDEWEB)

    Brenscheidt, T.; Wendt, H. [Institut fuer Chemische Technologie, Darmstadt (Germany)


    Since the early investigation of A. Klemm, the demixing of the cations of molten binary salt mixtures with a common anion due to the different mobilities of two different cations had been investigated in numerous experiments and the respective results interpreted in terms of structural features of the melts. 1-1 electrolytes had been preferentially investigated. Okada also reported investigations on lithium carbonate/potassium carbonate mixtures in the temperature range from 980 to 1070 K. From this investigation it is known that the heavier potassium cation is faster than lithium in mixtures which are more concentrated in potassium than x{sub K2CO3} = 0,32 (Chemla effect) whereas below this isotachic concentration lithium is faster. This paper investigates demixing in molten carbonate fuel cells.

  16. The Influence of Calcined Clay Pozzolan, Low-Cao Steel Slag and Granite Dust On the Alkali-Silica Reaction in Concrete

    Directory of Open Access Journals (Sweden)

    James Sarfo-Ansah


    Full Text Available The influence of low CaO steel slag, calcined clay and granite dust on the alkali-silica reaction was investigated over a period of 35 days under accelerated curing conditions. The mineral admixtures were used to replace varying portions of high alkali Portland limestone cement up to an admixture content of 25% in order to study their effect on the alkali-silica reaction (ASR. Portland limestone cement used for the study had a total Na2Oeq of 4.32. XRD analysis of hydrated mortar bar samples confirmed the formation of an expansive sodium silica gel in the reference Portland cement mortar bar as the agent responsible for ASR. Stable calcium silicates were formed in the mortar bars containing calcined clay in increasing quantities whilst the presence of the sodium silicate gel decreased.The occurrence of these stable silicates in hydrated samples containing steel slag and granite dust was however minimal, compared to calcined clay cement mortars. The highest expansion was recorded for granite dust mortar bars, reaching a maximum of 25.98% at 35 days. Mortar-bar expansion decreased as calcined clay content in the cement increased;mortar bars with 25% calcined clay were the least expansive recording expansion less than 0.1% at all test ages. Whilst the expansion was reduced by between 42.5% and 107.8% at 14 days with increasing calcined clay content, expansion rather increased between 36.8% and 169.5% at 14 days with increasing granite dust content.Steel slag mortar bars experienced reduction in 14 days expansion between 14.3% - 46.2%.The study confirms that steel slag and calcined clay pozzolan have greater influence on ASR in mortar bars than granite dust and shows that calcined clay and low CaO steel slag could be considered as remedial admixtures for ASR at replacement levels of 25% and 15% respectively.

  17. Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai E.

    studies of catalytic chemical reactions in dense and supercritical carbon dioxide have been complemented by the theoretical calculations of phase equilibria using advanced thermodynamic models. In the recent years, the use of compressed carbon dioxide as innovative, non-toxic and non-flammable, cheap...... is discussed more extensively. Heterogeneously catalysed hydrogenation reactions are considered to be quite well studied and established. However, the catalyst performance can alter significantly when the reaction is performed in carbon dioxide medium. This effect was studied with the example of the selective...... the selective hydrogenation of unsaturated aldehydes in carbon dioxide medium. It was found that supported tungstosilicic acid catalysts and acidic resin Amberlyst-15 are very effective for performing aldol reactions. The positive influence of temperature and CO2-content on catalyst activity was studied...

  18. Combined reactions and separations using ionic liquids and carbon dioxide

    NARCIS (Netherlands)

    Kroon, M.C.


    A new and general type of process for the chemical industry is presented using ionic liquids and supercritical carbon dioxide as combined reaction and separation media. In this process, the carbon dioxide pressure controls the miscibility of reactants, products, catalyst and ionic liquid, enabling f

  19. Effect of Carbon Containing Materials on Pure Carbon Reaction-bonded SiC

    Institute of Scientific and Technical Information of China (English)

    JI Xiaoli; WEI Lei; SUN Feng


    Petroleum coke, graphite, gas carbon and lower sulfur carbon black were used to prepare reaction-bonded silicon carbide. The influences of different carbon containing materials on properties of carbonaceous precursors, sintering process, and microstructure of the prepared SiC were researched. The results show that:(1)With the density of carbon containing materials increasing, the porosity of carbonaceous precursors decreases and the infiltrating process of liquid silicon is more difficult.(2)The reaction between carbon containing materials and liquid silicon, the volume effect is more obvious with the density of carbon containing materials increasing.(3)As the carbon containing materials density decreasing, residual carbon in reaction bonded SiC also decreases.

  20. Alkali control of high-grade metamorphism and granitization

    Directory of Open Access Journals (Sweden)

    Oleg G. Safonov


    Full Text Available We review petrologic observations of reaction textures from high-grade rocks that suggest the passage of fluids with variable alkali activities. Development of these reaction textures is accompanied by regular compositional variations in plagioclase, pyroxenes, biotite, amphibole and garnet. The textures are interpreted in terms of exchange and net-transfer reactions controlled by the K and Na activities in the fluids. On the regional scale, these reactions operate in granitized, charnockitized, syenitized etc. shear zones within high-grade complexes. Thermodynamic calculations in simple chemical systems show that changes in mineral assemblages, including the transition from the hydrous to the anhydrous ones, may occur at constant pressure and temperature due only to variations in the H2O and the alkali activities. A simple procedure for estimating the activity of the two major alkali oxides, K2O and Na2O, is implemented in the TWQ software. Examples of calculations are presented for well-documented dehydration zones from South Africa, southern India, and Sri Lanka. The calculations have revealed two end-member regimes of alkalis during specific metamorphic processes: rock buffered, which is characteristic for the precursor rocks containing two feldspars, and fluid-buffered for the precursor rocks without K-feldspar. The observed reaction textures and the results of thermodynamic modeling are compared with the results of available experimental studies on the interaction of the alkali chloride and carbonate-bearing fluids with metamorphic rocks at mid-crustal conditions. The experiments show the complex effect of alkali activities in the fluid phase on the mineral assemblages. Both thermodynamic calculations and experiments closely reproduce paragenetic relations theoretically predicted by D.S. Korzhinskii in the 1940s.

  1. Modeling Corrosion Reactions of Steel in a Dilute Carbonate Solution (United States)

    Eliyan, Faysal Fayez; Alfantazi, Akram


    This research models the corrosion reactions of a high-strength steel in an aerated, dilute, carbonate solution during a single-cycle voltammetry. Based on a previous study (Eliyan et al. in J Mater Eng Perform 24(6):1-8, 2015) and a literature survey, the corrosion reactions of the cathodic reduction, anodic dissolution, and passivation, as well as the interfacial interactions and the chemistry of the corrosion products are illustrated in schematics. The paper provides a visual guide on the corrosion reactions for steel in carbonate solutions based on the available mechanistic details that were reported and are still being investigated in literature.

  2. Carbon-Carbon Bond Cleavage Reaction: Synthesis of Multisubstituted Pyrazolo[1,5-a]pyrimidines. (United States)

    Saikia, Pallabi; Gogoi, Sanjib; Boruah, Romesh C


    A new carbon-carbon bond cleavage reaction was developed for the efficient synthesis of multisubstituted pyrazolo[1,5-a]pyrimidines. This base induced reaction of 1,3,5-trisubstituted pentane-1,5-diones and substituted pyrazoles afforded good yields of the pyrazolo[1,5-a]pyrimidines.

  3. Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions. (United States)

    Powell, Lyndsey R; Piao, Yanmei; Wang, YuHuang


    Covalent chemistries have been widely used to modify carbon nanomaterials; however, they typically lack the precision and efficiency required to directly engineer their optical and electronic properties. Here, we show, for the first time, that visible light which is tuned into resonance with carbon nanotubes can be used to drive their functionalization by aryldiazonium salts. The optical excitation accelerates the reaction rate 154-fold (±13) and makes it possible to significantly improve the efficiency of covalent bonding to the sp(2) carbon lattice. Control experiments suggest that the reaction is dominated by a localized photothermal effect. This light-driven reaction paves the way for precise nanochemistry that can directly tailor carbon nanomaterials at the optical and electronic levels.

  4. Reaction studies of hot silicon, germanium and carbon atoms

    Energy Technology Data Exchange (ETDEWEB)

    Gaspar, P.P.


    The goal of this project was to increase the authors understanding of the interplay between the kinetic and electronic energy of free atoms and their chemical reactivity by answering the following questions: (1) what is the chemistry of high-energy carbon silicon and germanium atoms recoiling from nuclear transformations; (2) how do the reactions of recoiling carbon, silicon and germanium atoms take place - what are the operative reaction mechanisms; (3) how does the reactivity of free carbon, silicon and germanium atoms vary with energy and electronic state, and what are the differences in the chemistry of these three isoelectronic atoms This research program consisted of a coordinated set of experiments capable of achieving these goals by defining the structures, the kinetic and internal energy, and the charge states of the intermediates formed in the gas-phase reactions of recoiling silicon and germanium atoms with silane, germane, and unsaturated organic molecules, and of recoiling carbon atoms with aromatic molecules. The reactions of high energy silicon, germanium, and carbon atoms created by nuclear recoil were studied with substrates chosen so that their products illuminated the mechanism of the recoil reactions. Information about the energy and electronic state of the recoiling atoms at reaction was obtained from the variation in end product yields and the extent of decomposition and rearrangement of primary products (usually reactive intermediates) as a function of total pressure and the concentration of inert moderator molecules that remove kinetic energy from the recoiling atoms and can induce transitions between electronic spin states. 29 refs.

  5. Unified ZnO Q-dot growth mechanism from simultaneous UV-Vis and EXAFS monitoring of sol-gel reactions induced by different alkali base (United States)

    Caetano, Bruno L.; Silva, Marlon N.; Santilli, Celso V.; Briois, Valérie; Pulcinelli, Sandra H.


    This article aims to give experimental evidences of the universality of main steps involved in ZnO nanoparticles formation and growth from sol-gel process. In this way, we revisit the effect of the alkali base (LiOH, NaOH, KOH) used to induce the hydrolysis-condensation reaction in order to unfold the ZnO Q-dot formation mechanisms by using simultaneous time resolved monitoring of zinc species and Q-dot size by combining EXAFS and UV-Vis spectroscopy. Irrespective of the alkali base used, nucleation and growth of ZnO Q-dots occur by consumption of zinc oxy-acetate precursor. Higher amounts of ZnO nanocrystal are produced as the strength of the base increases. After achieving the steady state equilibrium regime the Q-dot growth occurs initially by oriented attachment coalescence mechanism followed by the Ostwald ripening coarsening. The dependence of the formation and growth mechanisms on the base strength allows the fine tuning of the Q-dot size and photoluminescence properties.

  6. Interaction of Fe-Al-Cr-C with the melt of an alkali metal carbonate (United States)

    Nikitina, E. V.


    The interaction of an Fe-Al-Cr-C (29.5 wt % Fe, 29.35 wt % Cr, 2.56 wt % C, 38.59 wt % Al) alloy with the melt of a lithium, sodium, or potassium carbonate containing 1-5 wt % addition to a salt phase is studied by gravimetry and measuring the corrosion potential and anode polarization curves in the temperature range 500-600°C. As passivators, the substances that decrease the corrosion losses due to hardening and thickening of an oxide film (lithium, sodium, potassium hydroxides) are used. As corrosion stimulators (activators), sodium chloride, fluoride, and sulfate are used. The coalloying of iron with chromium and aluminum results in high corrosion resistance against both frontal (continuous) and local (pitting, intercrystalline) corrosion as a result of formation of chemically resistant and high-adhesion oxide layers with their participation. X-ray diffraction analysis reveals gamma aluminum oxide, spinel (alumochromite) traces, and lithium aluminate at the surface.

  7. Alkali metal ion catalysis and inhibition in nucleophilic displacement reactions at phosphorus centers: ethyl and methyl paraoxon and ethyl and methyl parathion. (United States)

    Um, Ik-Hwan; Shin, Young-Hee; Lee, Seung-Eun; Yang, Kiyull; Buncel, Erwin


    We report on the ethanolysis of the P=O and P=S compounds ethyl and methyl paraoxon (1a and 1b) and ethyl and methyl parathion (2a and 2b). Plots of spectrophotometrically measured rate constants, kobsd versus [MOEt], the alkali ethoxide concentration, show distinct upward and downward curvatures, pointing to the importance of ion-pairing phenomena and a differential reactivity of free ions and ion pairs. Three types of reactivity and selectivity patterns have been discerned: (1) For the P=O compounds 1a and 1b, LiOEt > NaOEt > KOEt > EtO-; (2) for the P=S compound 2a, KOEt > EtO- > NaOEt > LiOEt; (3) for P=S, 2b, 18C6-crown-complexed KOEt > KOEt = EtO(-) > NaOEt > LiOEt. These selectivity patterns are characteristic of both catalysis and inhibition by alkali-metal cations depending on the nature of the electrophilic center, P=O vs P=S, and the metal cation. Ground-state (GS) vs transition-state (TS) stabilization energies shed light on the catalytic and inhibitory tendencies. The unprecedented catalytic behavior of crowned-K(+) for the reaction of 2b is noteworthy. Modeling reveals an extreme steric interaction for the reaction of 2a with crowned-K(+), which is responsible for the absence of catalysis in this system. Overall, P=O exhibits greater reactivity than P=S, increasing from 50- to 60-fold with free EtO(-) and up to 2000-fold with LiOEt, reflecting an intrinsic P=O vs P=S reactivity difference (thio effect). The origin of reactivity and selectivity differences in these systems is discussed on the basis of competing electrostatic effects and solvational requirements as function of anionic electric field strength and cation size (Eisenman's theory).

  8. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard


    A method for removing sulfur, nitrogen or metals from an oil feedstock. The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  9. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard


    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  10. Reactions of carbon atoms in pulsed molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Reisler, H. [Univ. of Southern California, Los Angeles (United States)


    This research program consists of a broad scope of experiments designed to unravel the chemistry of atomic carbon in its two spin states, P and D, by using well-controlled initial conditions and state-resolved detection of products. Prerequisite to the proposed studies (and the reason why so little is known about carbon atom reactions), is the development of clean sources of carbon atoms. Therefore, in parallel with the studies of its chemistry and reaction dynamics, the authors continuously explore new, state-specific and efficient ways of producing atomic carbon. In the current program, C({sup 3}P) is produced via laser ablation of graphite, and three areas of study are being pursued: (i) exothermic reactions with small inorganic molecules (e.g., O{sub 2}, N{sub 2}O, NO{sub 2}) that can proceed via multiple pathways; (ii) the influence of vibrational and translational energy on endothermic reactions involving H-containing reactants that yield CH products (e.g., H{sub 2}O H{sub 2}CO); (iii) reactions of C({sup 3}P) with free radicals (e.g., HCO, CH{sub 3}O). In addition, the authors plan to develop a source of C({sup 1}D) atoms by exploiting the pyrolysis of diazotetrazole and its salts in the ablation source. Another important goal involves collaboration with theoreticians in order to obtain relevant potential energy surfaces, rationalize the experimental results and predict the roles of translational and vibrational energies.

  11. The Effect of Alkali Carbonate on the Catalytic Properties for Methane Conversion with Ce-Zr-O%碱金属碳酸盐掺杂的Ce-Zr-O对甲烷转化催化性能的影响

    Institute of Scientific and Technical Information of China (English)

    段月娟; 魏永刚; 李孔斋; 王华; 祝星; 杜云鹏


    Pure Ce-Zr-O mixed oxide was prepared via precipitation method, and catalysts doped with alkali carbonates (M2CO3, M=Li, Na, K) were prepared by incipient wetness impregnation methods. The catalytic activity for methane was investigated by the gas-solid reaction in a fixed bed reactor, and characterized by means of XRD and H2-TPR techniques. The results show that the catalytic activity of Ce-Zr-O is promoted with varied following the doping of alkali carbonates, the anti-coking and anti-sintering properties of the catalysts are enhanced, and the surface oxygen species and the bulk oxygen species of the catalysts are improved as well.%采用共沉淀法制备了Ce-Zr-O载体,通过等体积浸渍法得到碱金属碳酸盐掺杂的M2CO3/Ce-Zr-O(M=Li,Na,K)催化剂.采用自制的小型固定床反应器考察了催化剂的甲烷转化催化活性,并利用XRD和H2-TPR对催化剂进行了表征.研究结果表明,碱金属碳酸盐的添加均不同程度地提高了Ce-Zr-O催化剂的催化活性、抗积碳性能和抗烧结性能,还改善了催化剂表面氧物种和体相氧物种的氧化还原性能.

  12. Thermodynamics behind carbon nanotube growth via endothermic catalytic decomposition reaction. (United States)

    Harutyunyan, Avetik R; Kuznetsov, Oleg A; Brooks, Christopher J; Mora, Elena; Chen, Gugang


    Carbon filaments can be grown using hydrocarbons with either exothermic or endothermic catalytic decomposition enthalpies. By in situ monitoring the evolution of the reaction enthalpy during nanotube synthesis via methane gas, we found that although the decomposition reaction of methane is endothermic an exothermic process is superimposed which accompanies the nanotube growth. Analysis shows that the main contributor in this liberated heat is the radiative heat transfer from the surroundings, along with dehydrogenation reaction of in situ formed secondary hydrocarbons on the catalyst surface and the carbon hydrogenation/oxidation processes. This finding implies that nanotube growth process enthalpy is exothermic, and particularly, it extends the commonly accepted temperature gradient driven growth mechanism to the growth via hydrocarbons with endothermic decomposition enthalpy.

  13. Study on alkali reaction of nickel slag and nickel slag-sand mixtures in Ningde region%宁德地区镍渣及其复掺砂的碱活性研究

    Institute of Scientific and Technical Information of China (English)



    The article discussed the alkali reaction of nickel slag and aggregate mixed with natural sand through petrographic method and al -kali-aggregate reaction .The results showed that the nickel slag could not be used as aggregate in concrete because of its potential alkali -aggregate damage .The research also showed that the potential alkali -aggregate damage could be reduced by mixing natural sand , and there was no alkali-aggregate harm to the aggregate when the natural sand content was not less than 50%.%本文通过岩相法和快速碱-骨料反应法研究了镍渣及其复掺砂的碱活性。研究表明镍渣具有潜在碱-骨料反应危害,不宜单独用作混凝土骨料。通过复掺标准砂可以降低碱-骨料反应危害,实验表明当标准砂掺量不低于50%时,复掺砂不存在碱-骨料反应危害。

  14. Diffusion-reaction compromise the polymorphs of precipitated calcium carbonate

    Institute of Scientific and Technical Information of China (English)

    Han Wang; Wenlai Huang; Yongsheng Han


    Diffusion is seldom considered by chemists and materialists in the preparation of materials while it plays an important role in the field of chemical engineering.If we look at crystallization at the atomic level,crystal growth in a solution starts from the diffusion of ions to the growing surface followed by the incorporation of ions into its lattice.Diffusion can be a rate determining step for the growth of crystals.In this paper,we take the crystallization of calcium carbonate as an example to illustrate the microscopic processes of diffusion and reaction and their compromising influence on the morphology of the crystals produced.The diffusion effect is studied in a specially designed three-cell reactor.Experiments show that a decrease of diffusion leads to retardation of supersaturation and the formation of a continuous concentration gradient in the reaction cell,thus promoting the formation of cubic calcite particles.The reaction rate is regulated by temperature.Increase of reaction rate favors the formation of needle-like aragonite particles.When diffusion and reaction play joint roles in the reaction system,their compromise dominates the formation of products,leading to a mixture of cubic and needle-like particles with a controllable ratio.Since diffusion and reaction are universal factors in the preparation of materials,the finding of this paper could be helpful in the controlled synthesis of other materials.

  15. Use of alkali metal salts to prepare high purity single-walled carbon nanotube solutions and thin films (United States)

    Ashour, Rakan F.

    Single-walled carbon nanotubes (SWCNTs) display interesting electronic and optical properties desired for many advanced thin film applications, such as transparent conductive electrodes or thin-film transistors. Large-scale production of SWCNTs generally results in polydispersed mixtures of nanotube structures. Since SWCNT electronic character (conducting or semiconducting nature) depends on the nanotube structure, application performance is being held back by this inability to discretely control SWCNT synthesis. Although a number of post-production techniques are able to separate SWCNTs based on electronic character, diameter, or chirality, most still suffer from the disadvantage of high costs of materials, equipment, or labor intensity to be relevant for large-scale production. On the other hand, chromatographic separation has emerged as a method that is compatible with large scale separation of metallic and semiconducting SWCNTs. In this work, SWCNTs, in an aqueous surfactant suspension of sodium dodecyl sulfate (SDS), are separated by their electronic character using a gel chromatography process. Metallic SWCNTs (m-SWCNTs) are collected as initial fractions since they show minimum interaction with the gel medium, whereas, semiconducting SWCNTs (sc- SWCNTs) remain adsorbed to the gel. The process of sc-SWCNT retention in the gel is found to be driven by the packing density of SDS around the SWCNTs. Through a series of separation experiments, it is shown that sc-SWCNTs can be eluted from the gel simply by disturbing the configuration of the SDS/SWCNT micellar structure. This is achieved by either introducing a solution containing a co-surfactant, such as sodium cholate (SC), or solutions of alkali metal ionic salts. Analysis of SWCNT suspensions by optical absorption provides insights into the effect of changing the metal ion (M+ = Li+, Na+, and K+) in the eluting solution. Salts with smaller metal ions (e.g. Li+) require higher concentrations to achieve

  16. Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Um, Wooyong; Jung, Hun Bok; Martin, Paul F.; McGrail, B. Peter


    Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C) for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron

  17. Carbon encapsulated magnetic nanoparticles produced by hydrothermal reaction

    Institute of Scientific and Technical Information of China (English)

    Nong Yue He; Ya Fei Guo; Yan Deng; Zhi Fei Wang; Song Li; Hong Na Liu


    Carbon encapsulated magnetic nanoparticles (CEMNs) were synthesized by heating an aqueous glucose solution containing FeAu (Au coated Fe nanoparticles) nanoparticles at 160-180 ℃ for 2 h. This novel hydrothermal approach is not only simple but also provides the surface of CEMNs with functional groups like-OH. The formation of carbon encapsulated magnetic nanoparticles was not favored when using pure Fe nanoparticles as cores because of the oxidation of Fe nanoparticles by H2O during the reaction and,therefore, the surfaces of the naked Fe nanoparticles had to be coated by Au shell in advance. TEM, XRD, XPS and VSM measurments characterized that they were uniform carbon spheres containing some embedded Fe-Au nanoparticles, with a saturation of 14.6 emu/g and the size of the typical product is ~350 nm.

  18. Chemical Reactions in the Processing of Mosi2 + Carbon Compacts (United States)

    Jacobson, Nathan S.; Lee, Kang N.; Maloy, Stuart A.; Heuer, Arthur H.


    Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

  19. Alkali-silica reactions of mortars produced by using waste glass as fine aggregate and admixtures such as fly ash and Li2CO3. (United States)

    Topçu, Ilker Bekir; Boğa, Ahmet Raif; Bilir, Turhan


    Use of waste glass or glass cullet (GC) as concrete aggregate is becoming more widespread each day because of the increase in resource efficiency. Recycling of wastes is very important for sustainable development. When glass is used as aggregate in concrete or mortar, expansions and internal stresses occur due to an alkali-silica reaction (ASR). Furthermore, rapid loss in durability is generally observed due to extreme crack formation and an increase in permeability. It is necessary to use some kind of chemical or mineral admixture to reduce crack formation. In this study, mortar bars are produced by using three different colors of glass in four different quantities as fine aggregate by weight, and the effects of these glass aggregates on ASR are investigated, corresponding to ASTM C 1260. Additionally, in order to reduce the expansions of mortars, 10% and 20% fly ash (FA) as mineral admixture and 1% and 2% Li(2)CO(3) as chemical admixture are incorporated by weight in the cement and their effects on expansion are examined. It is observed that among white (WG), green (GG) and brown glass (BG) aggregates, WG aggregate causes the greatest expansion. In addition, expansion increases with an increase in amount of glass. According to the test results, it is seen that over 20% FA and 2% Li(2)CO(3) replacements are required to produce mortars which have expansion values below the 0.2% critical value when exposed to ASR. However, usages of these admixtures reduce expansions occurring because of ASR.

  20. GRIZZLY Model of Multi-Reactive Species Diffusion, Moisture/Heat Transfer and Alkali-Silica Reaction for Simulating Concrete Aging and Degradation

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Hai [Idaho National Lab. (INL), Idaho Falls, ID (United States); Spencer, Benjamin W. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cai, Guowei [Vanderbilt Univ., Nashville, TN (United States)


    Concrete is widely used in the construction of nuclear facilities because of its structural strength and its ability to shield radiation. The use of concrete in nuclear power plants for containment and shielding of radiation and radioactive materials has made its performance crucial for the safe operation of the facility. As such, when life extension is considered for nuclear power plants, it is critical to have accurate and reliable predictive tools to address concerns related to various aging processes of concrete structures and the capacity of structures subjected to age-related degradation. The goal of this report is to document the progress of the development and implementation of a fully coupled thermo-hydro-mechanical-chemical model in GRIZZLY code with the ultimate goal to reliably simulate and predict long-term performance and response of aged NPP concrete structures subjected to a number of aging mechanisms including external chemical attacks and volume-changing chemical reactions within concrete structures induced by alkali-silica reactions and long-term exposure to irradiation. Based on a number of survey reports of concrete aging mechanisms relevant to nuclear power plants and recommendations from researchers in concrete community, we’ve implemented three modules during FY15 in GRIZZLY code, (1) multi-species reactive diffusion model within cement materials; (2) coupled moisture and heat transfer model in concrete; and (3) anisotropic, stress-dependent, alkali-silica reaction induced swelling model. The multi-species reactive diffusion model was implemented with the objective to model aging of concrete structures subjected to aggressive external chemical attacks (e.g., chloride attack, sulfate attack, etc.). It considers multiple processes relevant to external chemical attacks such as diffusion of ions in aqueous phase within pore spaces, equilibrium chemical speciation reactions and kinetic mineral dissolution/precipitation. The moisture

  1. RILEM recommendations for the prevention of damage by alkali-aggregate reactions in new concrete structures state-of-the-art report of the RILEM technical committee 219-ACS

    CERN Document Server

    Sims, Ian


    This book contains the full set of RILEM Recommendations which have been produced to enable engineers, specifiers and testing houses to design and produce concrete which will not suffer damage arising from alkali reactions in the concrete. There are five recommended test methods for aggregates (designated AAR-1 to AAR-5), and an overall recommendation which describes how these should be used to enable a comprehensive aggregate assessment (AAR-0). Additionally, there are two Recommended International Specifications for concrete (AAR-7.1 & 7.2) and a Preliminary International Specification for dams and other hydro structures (AAR-7.3), which describe how the aggregate assessment can be combined with other measures in the design of the concrete to produce a concrete with a minimised risk of developing damage from alkali-aggregate reactions.

  2. Preparation of Cyclic Urethanes from Amino Alcohols and Carbon Dioxide Using Ionic Liquid Catalysts with Alkali Metal Promoters

    Directory of Open Access Journals (Sweden)

    Masahiko Arai


    Full Text Available Several ionic liquids were applied as catalysts for the synthesis of cyclicurethanes from amino alcohols and pressurized CO2 in the presence of alkali metalcompounds as promoters. A comparative study was made for the catalytic performanceusing different ionic liquids, substrates, promoters, and pressures. The optimum catalyticsystem was BMIM-Br promoted by K2CO3, which, for 1-amino-2-propanol, produced cyclicurethane in 40% yield with a smaller yield of substituted cyclic urea and no oligomericbyproducts. For other amino alcohols, cyclic urethanes, cyclic ureas, and/or undesiredbyproducts were produced in different yields depending on the substrates used. Possiblereaction mechanisms are proposed.

  3. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions (United States)

    Cortright, Randy D.; Dumesic, James A.


    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  4. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions (United States)

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI


    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  5. Analysis of carbon partitioning during ausferritic reaction in ADI

    Directory of Open Access Journals (Sweden)

    Z. Ławrynowicz


    Full Text Available The investigation was carried out to examine the influence of temperature and times of austempering process on the maximum extend towhich the ausferritic reaction can proceed and the carbon content in retained austenite. Specimens prepared from ductile cast iron wereaustenitised at 950oC for 60 minutes and austempered at four temperatures: 250, 300, 350 and 400oC. The samples were austempered atthese temperatures for 15, 30, 60, 120 and 240 minutes and finally quenched to ambient temperature. Volume fractions of retainedaustenite and carbon concentration in the residual austenite have been observed by using X-ray diffraction. Additionally, carbonconcentration in the residual austenite was calculated using volume fraction data of austenite and a model developed by Bhadeshia basedon the McLellan and Dunn quasi-chemical thermodynamic model. It was found that the obtained extend of ausferritic transformation isonly possible when the microstructure consists of not only ausferrite but additionally precipitated carbides.

  6. Application of micro X-ray diffraction to investigate the reaction products formed by the alkali silica reaction in concrete structures

    Energy Technology Data Exchange (ETDEWEB)

    Dähn, R.; Arakcheeva, A.; Schaub, Ph.; Pattison, P.; Chapuis, G.; Grolimund, D.; Wieland, E.; Leemann, A. (Ecole); (PSI); (Phase Solutions); (ESRF)


    Alkali–silica reaction (ASR) is one of the most important deterioration mechanisms in concrete leading to substantial damages of structures worldwide. Synchrotron-based micro-X-ray diffraction (micro-XRD) was employed to characterize the mineral phases formed in micro-cracks of concrete aggregates as a consequence of ASR. This particular high spatial resolution technique enables to directly gain structural information on ASR products formed in a 40-year old motorway bridge damaged due to ASR. Micro-X-ray-fluorescence was applied on thin sections to locate the reaction products formed in veins within concrete aggregates. Micro-XRD pattern were collected at selected points of interest along a vein by rotating the sample. Rietveld refinement determined the structure of the ASR product consisting of a new layered framework similar to mountainite and rhodesite. Furthermore, it is conceivable that understanding the structure of the ASR product may help developing new technical treatments inhibiting ASR.

  7. Device and method for upgrading petroleum feedstocks and petroleum refinery streams using an alkali metal conductive membrane

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier


    A reactor has two chambers, namely an oil feedstock chamber and a source chamber. An ion separator separates the oil feedstock chamber from the source chamber, wherein the ion separator allows alkali metal ions to pass from the source chamber, through the ion separator, and into the oil feedstock chamber. A cathode is at least partially housed within the oil feedstock chamber and an anode is at least partially housed within the source chamber. A quantity of an oil feedstock is within the oil feedstock chamber, the oil feedstock comprising at least one carbon atom and a heteroatom and/or one or more heavy metals, the oil feedstock further comprising naphthenic acid. When the alkali metal ion enters the oil feedstock chamber, the alkali metal reacts with the heteroatom, the heavy metals and/or the naphthenic acid, wherein the reaction with the alkali metal forms inorganic products.

  8. Mineral carbonation of gaseous carbon dioxide using a clay-hosted cation exchange reaction. (United States)

    Kang, Il-Mo; Roh, Ki-Min


    The mineral carbonation method is still a challenge in practical application owing to: (1) slow reaction kinetics, (2) high reaction temperature, and (3) continuous mineral consumption. These constraints stem from the mode of supplying alkaline earth metals through mineral acidification and dissolution. Here, we attempt to mineralize gaseous carbon dioxide into calcium carbonate, using a cation exchange reaction of vermiculite (a species of expandable clay minerals). The mineralization is operated by draining NaCI solution through vermiculite powders and continuously dropping into the pool of NaOH solution with CO2 gas injected. The mineralization temperature is regulated here at 293 and 333 K for 15 min. As a result of characterization, using an X-ray powder diffractometer and a scanning electron microscopy, two types of pure CaCO3 polymorphs (vaterite and calcite) are identified as main reaction products. Their abundance and morphology are heavily dependent on the mineralization temperature. Noticeably, spindle-shaped vaterite, which is quite different from a typical vaterite morphology (polycrystalline spherulite), forms predominantly at 333 K (approximately 98 wt%).

  9. Photoionization in alkali lasers. (United States)

    Knize, R J; Zhdanov, B V; Shaffer, M K


    We have calculated photoionization rates in alkali lasers. The photoionization of alkali atoms in the gain medium of alkali lasers can significantly degrade the laser performance by reducing the neutral alkali density and with it the gain. For a ten atmosphere Rb laser and a Cs exciplex laser, the photoionization induced alkali atom loss rates are greater than 10(5) sec(-1). These high loss rates will quickly deplete the neutral alkali density, reducing gain, and may require fast, possibly, supersonic flow rates to sufficiently replenish the neutral medium for CW operation.

  10. Chapter K: Progress in the Evaluation of Alkali-Aggregate Reaction in Concrete Construction in the Pacific Northwest, United States and Canada (United States)

    Shrimer, Fred H.


    The supply of aggregates suitable for use in construction and maintenance of infrastructure in western North America is a continuing concern to the engineering and resources-management community. Steady population growth throughout the region has fueled demand for high-quality aggregates, in the face of rapid depletion of existing aggregate resources and slow and difficult permitting of new sources of traditional aggregate types. In addition to these challenges, the requirement for aggregates to meet various engineering standards continues to increase. In addition to their physical-mechanical properties, other performance characteristics of construction aggregates specifically depend on their mineralogy and texture. These properties can result in deleterious chemical reactions when aggregate is used in concrete mixes. When this chemical reaction-termed 'alkali-aggregate reaction' (AAR)-occurs, it can pose a major problem for concrete structures, reducing their service life and requiring expensive repair or even replacement of the concrete. AAR is thus to be avoided in order to promote the longevity of concrete structures and to ensure that public moneys invested in infrastructure are well spent. Because the AAR phenomenon is directly related to the mineral composition, texture, and petrogenesis of the rock particles that make up aggregates, an understanding of the relation between the geology and the performance of aggregates in concrete is important. In the Pacific Northwest, some aggregates have a moderate to high AAR potential, but many others have no or only a low AAR potential. Overall, AAR is not as widespread or serious a problem in the Pacific Northwest as in other regions of North America. The identification of reactive aggregates in the Pacific Northwest and the accurate prediction of their behavior in concrete continue to present challenges for the assessment and management of geologic resources to the owners and operators of pits and quarries and to the

  11. Electrochemical device for converting carbon dioxide to a reaction product

    Energy Technology Data Exchange (ETDEWEB)

    Masel, Richard I.; Chen, Qingmei; Liu, Zengcai; Kutz, Robert


    An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potential of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.

  12. Milk-alkali syndrome (United States)

    ... this page: // Milk-alkali syndrome To use the sharing features on this page, please enable JavaScript. Milk-alkali syndrome is a condition in which there ...

  13. Complete reaction mechanisms of mercury oxidation on halogenated activated carbon. (United States)

    Rungnim, Chompoonut; Promarak, Vinich; Hannongbua, Supa; Kungwan, Nawee; Namuangruk, Supawadee


    The reaction mechanisms of mercury (Hg) adsorption and oxidation on halogenated activated carbon (AC) have been completely studied for the first time using density functional theory (DFT) method. Two different halogenated AC models, namely X-AC and X-AC-X (X=Cl, Br, I), were adopted. The results revealed that HgX is found to be stable-state on the AC edge since its further desorption from the AC as HgX, or further oxidation to HgX2, are energetically unfavorable. Remarkably, the halide type does not significantly affect the Hg adsorption energy but it strongly affects the activation energy barrier of HgX formation, which obviously increases in the order HgIBr-AC>Cl-AC. Thus, the study of the complete reaction mechanism is essential because the adsorption energy can not be used as a guideline for the rational material design in the halide impregnated AC systems. The activation energy is an important descriptor for the predictions of sorbent reactivity to the Hg oxidation process.

  14. Behavior of shungite carbon in reactions simulating thermal transformations of coal

    Energy Technology Data Exchange (ETDEWEB)

    Grigor' eva, E.N.; Rozhkova, N.N. [Russian Academy of Science, Moscow (Russian Federation)


    The catalytic activity of shungite carbon in reactions of model compounds (tetralin and benzyl phenyl ether) simulating thermolysis of coal was studied. The orders, rate constants, and activation energies of reactions were determined.

  15. High effective silica fume alkali activator

    Indian Academy of Sciences (India)

    Vladimír Živica


    Growing demands on the engineering properties of cement based materials and the urgency to decrease unsuitable ecologic impact of Portland cement manufacturing represent significant motivation for the development of new cement corresponding to these aspects. One category represents prospective alkali activated cements. A significant factor influencing their properties is alkali activator used. In this paper we present a new high effective alkali activator prepared from silica fume and its effectiveness. According to the results obtained this activator seems to be more effective than currently used activators like natrium hydroxide, natrium carbonate, and water glass.

  16. Deformation Behaviour of Geopolymer Mortars with Alkali-reactive Carbonate Aggregate%含碱活性碳酸盐骨料地质聚合物砂浆的变形行为

    Institute of Scientific and Technical Information of China (English)

    郑彦增; 卢都友; 刘永道; 许仲梓


    为探究传统碱–碳酸盐反应(ACR)机理和碱活性碳酸盐骨料在地质聚合物中的反应行为,对比研究了含纯白云石(YT)和含加拿大 Kingston 白云质灰岩(CK)地质聚合物砂浆分别在不同养护条件[室温相对湿度(RH)大于 95%、38 ℃时 RH〉95%和 80 ℃时 1mol/L NaOH 溶液]下的变形行为。结果显示:YT 在 3 种养护条件地质聚合物中仅起填料作用而使砂浆收缩略有减小;含 CK 地质聚合物砂浆随温度和/或碱度变化呈现显著不同的变形行为,特别是在 38 ℃、RH 〉 95%和 80 ℃、1 mol/L NaOH 溶液条件下分别于不同养护阶段产生微小膨胀;预示 CK 在地质聚合物体系中的反应机制可能与硅酸盐水泥体系中的显著不同,通过选择特定的碳酸盐骨料和养护条件,可望实现地质聚合物体系变形的调控%For understanding the alkali-carbonate reactivity in geopolymer and the mechanism of traditional alkali-carbonate reaction (ACR), the deformation behavior of geopolymer mortar with pure dolomite (YT) and dolomitic limestone from Kingston, Canada (CK) was studied by curing at different conditions, i.e. room tenaperature with over 95% relative humidity (RH), 38 ℃ RH 〉 95% and 80 ℃ 1 mol/L NaOH. Results show that, at the three curing conditions, YT only acts as a filler to slightly reduce the shrinkage of the mortar; The deformation behavior of geopolymer mortar with CK varies remarkably with the changes in the curing temperature and alkalinity, especially the mortars with CK expand slightly at different curing stages when cured at 38 ℃ RH〉95% and 80 ℃ 1 mol/L NaOH; it suggests that the reaction mechanism of CK in geopolymer may be quite different with that in cement system, and the shrinkage of geopolymer might be compensated by selecting special carbonate aggregate and curing conditions.

  17. [Characteristics of 'salt island' and 'fertile island' for Tamarix chinensis and soil carbon, nitrogen and phosphorus ecological stoichiometry in saline-alkali land]. (United States)

    Zhang, Li-hua; Chen, Xiao-bing


    To clarify the nutrient characteristics of 'salt island' and 'fertile island' effects in saline-alkali soil, the native Tamarix chinensis of the Yellow River Delta (YRD) was selected to measure its soil pH, electrical conductivity (EC), organic carbon (SOC), total nitrogen (N), total phosphorus (P) and their stoichiometry characteristics at different soil depths. The results showed that soil pH and EC increased with the increasing soil depth. Soil EC and P in the 0-20 cm layer decreased and increased from canopied area to interspace, respectively. SOC, N, N/P and C/P in the 20-40 cm soil layer decreased, and C/N increased from the shrub center to interspace. SOC and N contents between island and interspace both decreased but P content decreased firstly and then increased with the increasing soil depth. Soil pH correlated positively with EC. In addition, pH and EC correlated negatively with C, N, P contents and their ecological stoichiometry.

  18. Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions. (United States)

    Motokura, Ken; Tomita, Mitsuru; Tada, Mizuki; Iwasawa, Yasuhiro


    Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.

  19. Study on Utilization of Carboxyl Group Decorated Carbon Nanotubes and Carbonation Reaction for Improving Strengths and Microstructures of Cement Paste

    Directory of Open Access Journals (Sweden)

    Xiantong Yan


    Full Text Available Carbon nanotubes (CNTs have excellent mechanical properties and can be used to reinforce cement-based materials. On the other hand, the reaction product of carbonation with hydroxides in hydrated cement paste can reduce the porosity of cement-based materials. In this study, a novel method to improve the strength of cement paste was developed through a synergy of carbon nanotubes decorated with carboxyl group and carbonation reactions. The experimental results showed that the carboxyl group (–COOH of decorated carbon nanotubes and the surfactant can control the morphology of the calcium carbonate crystal of carbonation products in hydrated cement paste. The spindle-like calcium carbonate crystals showed great morphological differences from those observed in the conventional carbonation of cement paste. The spindle-like calcium carbonate crystals can serve as fiber-like reinforcements to reinforce the cement paste. By the synergy of the carbon nanotubes and carbonation reactions, the compressive and flexural strengths of cement paste were significantly improved and increased by 14% and 55%, respectively, when compared to those of plain cement paste.

  20. A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Young, Alan; Colbow, Vesna; Harvey, David; Rogers, Erin; Wessel, Silvia


    The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

  1. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian


    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  2. The role of metal centres in reduction and carboxylation reactions utilizing carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Aresta, M.; Quaranta, E.; Tommasi, I. (Bari Univ. (Italy))


    The utilisation of carbon dioxide in synthesis of chemicals has been confined for a long time essentially to urea and salicylic acid synthesis. Quite recently, after the discovery of transition metal-carbon dioxide complexes, the direct carboxylation of organic substrates has been investigated, the reactions can be categorized as: functionalization of olefins, CO[sub 2] insertion into C-H bond via C-H activation, reaction with strained rings, reaction with amines to afford carbamates, synthesis or organic carbonates via reaction with oxetanes. (A.B.). 41 refs, 8 figs., 2 tabs.

  3. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates. (United States)

    McDougal, Nolan T; Virgil, Scott C; Stoltz, Brian M


    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  4. Hybrid direct carbon fuel cells and their reaction mechanisms - a review

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Kammer Hansen, Kent


    with carbon capture and storage (CCS) due to the high purity of CO2 emitted in the exhaust gas. Direct carbon (or coal) fuel cells (DCFCs) are directly fed with solid carbon to the anode chamber. The fuel cell converts the carbon at the anode and the oxygen at the cathode into electricity, heat and reaction...... is discussed on the fuel cell stack and system levels. The range of DCFC types can be roughly broken down into four fuel cell types: aqueous hydroxide, molten hydroxide, molten carbonate and solid oxide fuel cells. Emphasis is placed on the electrochemical reactions occurring at the anode and the proposed...... mechanism(s) of these reactions for molten carbonate, solid oxide and hybrid direct carbon fuel cells. Additionally, the criteria of choosing the ‘best’ DCFC technology is explored, including system design (continuous supply of solid fuel), performance (power density, efficiency), environmental burden...

  5. Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction (United States)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian; Shen, Yuhua


    Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) -doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m2/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and addresses the disposal issue of waste biomass simultaneously for environment clean.

  6. Controllable-nitrogen doped carbon layer surrounding carbon nanotubes as novel carbon support for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, P.L.; Hsu, C.H.; Wu, H.M.; Hsu, W.S. [Department of Chemical Engineering, National Cheng Kung University, Tainan (China); Kuo, D. [Department of Biochemistry, University of Washington, Seattle, WA (United States)


    Novel nitrogen-doped carbon layer surrounding carbon nanotubes composite (NC-CNT) (N/C ratio 3.3-14.3 wt.%) as catalyst support has been prepared using aniline as a dispersant to carbon nanotubes (CNTs) and as a source for both carbon and nitrogen coated on the surface of the CNTs, where the amount of doped nitrogen is controllable. The NC-CNT so obtained were characterized with scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption and desorption isotherms. A uniform dispersion of Pt nanoparticles (ca. 1.5-2.0 nm) was then anchored on the surface of NC-CNT by using aromatic amine as a stabilizer. For these Pt/NC-CNTs, cyclic voltammogram measurements show a high electrochemical activity surface area (up to 103.7 m{sup 2} g{sup -1}) compared to the commercial E-TEK catalyst (55.3 m{sup 2} g{sup -1}). In single cell test, Pt/NC-CNT catalyst has greatly enhanced catalytic activity toward the oxygen reduction reaction, resulting in an enhancement of ca. 37% in mass activity compared with that of E-TEK. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Graphitic mesoporous carbon based on aromatic polycondensation as catalyst support for oxygen reduction reaction (United States)

    Liu, Peng; Kong, Jiangrong; Liu, Yaru; Liu, Qicheng; Zhu, Hongze


    Mesoporous carbon is constructed by monolithic polyaromatic mesophase deriving from the hexane insoluble of coal-tar pitch. This carbon material exhibits spherical morphology and layered crystallite, and thereby can be graphitized at 900 °C without destroying the mesoporous structure. Electrochemical measurements indicate that graphitic mesoporous carbon (GMC) support not only improves the activity of Pt electrocatalyst to oxygen reduction reaction (ORR), but also shows higher corrosion resistance than commercial XC-72 carbon black in the acid cathode environment.

  8. Carbon catalysis of reactions in the lithium SOCl2 and SO2 systems (United States)

    Kilroy, W. P.


    Certain hazards associated with lithium batteries have delayed widespread acceptance of these power sources. The reactivity of ground lithium carbon mixtures was examined. The effect of carbon types on this reactivity was determined. The basic reaction involved mixtures of lithium and carbon with battery electrolyte. The various parameters that influenced this reactivity included: the nature and freshness of the carbon; the freshness, the purity, and the conductive salt of the electrolyte; and the effect of Teflon or moisture.

  9. Carbon dioxide released from subduction zones by fluid-mediated reactions (United States)

    Ague, Jay J.; Nicolescu, Stefan


    The balance between the subduction of carbonate mineral-bearing rocks into Earth's mantle and the return of CO2 to the atmosphere by volcanic and metamorphic degassing is critical to the carbon cycle. Carbon is thought to be released from subducted rocks mostly by simple devolatilization reactions. However, these reactions will also retain large amounts of carbon within the subducting slab and have difficulty in accounting for the mass of CO2 emitted from volcanic arcs. Carbon release may therefore occur via fluid-induced dissolution of calcium carbonate. Here we use carbonate δ18O and δ13C systematics, combined with analyses of rock and fluid inclusion mineralogy and geochemistry, to investigate the alteration of the exhumed Eocene Cycladic subduction complex on the Syros and Tinos islands, Greece. We find that in marble rocks adjacent to two fluid conduits that were active during subduction, the abundance of calcium carbonate drastically decreases approaching the conduits, whereas silicate minerals increase. Up to 60-90% of the CO2 was released from the rocks--far greater than expected via simple devolatilization reactions. The δ18O of the carbonate minerals is 5-10 lighter than is typical for metamorphosed carbonate rocks, implying that isotopically light oxygen was transported by fluid infiltration from the surroundings. We suggest that fluid-mediated carbonate mineral removal, accompanied by silicate mineral precipitation, provides a mechanism for the release of enormous amounts of CO2 from subduction zones.

  10. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway. (United States)

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng


    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

  11. The Path of Carbon in Photosynthesis IX. Photosynthesis, Photoreduction, and the Hydrogen-Oxygen-Carbon Dioxide Dark Reaction (United States)

    Badin, E. J.; Calvin, M.


    A comparison of the rates of fixation of Carbon 14 dioxide in algae for the processes of photosynthesis, photoreduction and the hydrogen-oxygen-carbon dioxide dark reaction has been made. For the same series of experiments, rates of incorporation of tracer carbon into the separate soluble components using the radiogram method have been determined. The mechanism of carbon dioxide uptake has been shown to occur via two distinct paths. In all cases studied, essentially the same compounds appear radioactive. The distribution with time, however, differs markedly.

  12. Alkali cation specific adsorption onto fcc(111) transition metal electrodes. (United States)

    Mills, J N; McCrum, I T; Janik, M J


    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  13. The role of carbon in the photocatalytic reaction of carbon/TiO{sub 2} photocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Teng, Feng; Zhang, Guozhi; Wang, Youqing; Gao, Caitian; Chen, Lulu; Zhang, Peng; Zhang, Zhenxing, E-mail:; Xie, Erqing, E-mail:


    Graphical abstract: - Highlights: • Carbon/TiO{sub 2} composites were fabricated by one-step carbonization method. • Carbon was generated by the dehydration carbonation effect of polymers. • Carbon was formed inside and outside of the TiO{sub 2} nanoparticles. • The photocatalytic activities of the composites depend on the coating carbon. - Abstract: The carbon/TiO{sub 2} nanocomposites were fabricated by a simple one-step carbonization method with different polymers as precursors. Due to the dehydration carbonation effect of polymers, carbon was formed inside and outside of the TiO{sub 2} nanoparticles. The photo-degradation study of rhodamine B was carried out under UV–vis light irradiation, and the photocatalytic activities of carbon/TiO{sub 2} nanocomposites are affected severely by the state of carbon, including dopants and coatings. The results show that the carbon on the surface plays more important role in the photocatalytic process.

  14. Radical scavenging reaction kinetics with multiwalled carbon nanotubes

    NARCIS (Netherlands)

    Tsuruoka, Shuji; Matsumoto, Hidetoshi; Koyama, Kenichi; Akiba, Eiji; Yanagisawa, Takashi; Cassee, Flemming R.; Saito, Naoto; Usui, Yuki; Kobayashi, Shinsuke; Porter, Dale W.; Castranova, Vincent; Endo, Morinobu


    Progress in the development of carbon nanotubes (CNTs) has stimulated great interest among industries providing new applications. Meanwhile, toxicological evaluations on nanomaterials are advancing leading to a predictive exposure limit for CNTs, which implies the possibility of designing safer CNTs

  15. Growth and Destruction of PAH Molecules in Reactions with Carbon Atoms (United States)

    Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia; Henning, Thomas


    A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that all small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.

  16. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase. (United States)

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping


    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture.

  17. Somewhere beyond the sea? The oceanic - carbon dioxide - reactions (United States)

    Meisinger, Philipp; Wittlich, Christian


    In correlation to climate change and CO2 emission different campaigns highlight the importance of forests and trees to regulate the concentration of carbon dioxide in the earths' atmosphere. Seeing millions of square miles of rainforest cut down every day, this is truly a valid point. Nevertheless, we often tend to forget what scientists like Spokes try to raise awareness for: The oceans - and foremost deep sea sections - resemble the second biggest deposit of carbon dioxide. Here carbon is mainly found in form of carbonate and hydrogen carbonate. The carbonates are needed by corals and other sea organisms to maintain their skeletal structure and thereby to remain vital. To raise awareness for the protection of this fragile ecosystem in schools is part of our approach. Awareness is achieved best through understanding. Therefore, our approach is a hands-on activity that aims at showing students how the carbon dioxide absorption changes in relation to the water temperature - in times of global warming a truly sensitive topic. The students use standard syringes filled with water (25 ml) at different temperatures (i.e. 10°C, 20°C, 40°C). Through a connector students inject carbon dioxide (25ml) into the different samples. After a fixed period of time, students can read of the remaining amount of carbon dioxide in relation to the given water temperature. Just as with every scientific project, students need to closely monitor their experiments and alter their setups (e.g. water temperature or acidity) according to their initial planning. A digital template (Excel-based) supports the analysis of students' experiments. Overview: What: hands-on, minds -on activity using standard syringes to exemplify carbon dioxide absorption in relation to the water temperature (Le Chatelier's principle) For whom: adjustable from German form 11-13 (age: 16-19 years) Time: depending on the prior knowledge 45-60 min. Sources (extract): Spokes, L.: Wie Ozeane CO2 aufnehmen. Environmental

  18. Comparison of mass loss rate in reaction of silica with carbon from different investigation results

    Directory of Open Access Journals (Sweden)

    J. Węgrzyn


    Full Text Available In the process of carbothermic reaction of SiO2 + mC, key reactions appear on the surfaces of both SiO2 and C grains. However, the values of these surfaces are not known. Assuming the simplest case, quartzite and carbon grains are spheres, total surfaces of reaction were calculated for grains of carbon and quartzite respectively. This enabled to determine the rate of weight loss referred to the unit area of C and SiO2.

  19. Mechanochemical Reaction of Lanthanum Carbonate with Sodium Hydroxide and Preparation of Lanthanum Oxide Nanoparticle

    Institute of Scientific and Technical Information of China (English)

    李永绣; 周雪珍; 王志强


    The preparation of nano sized La2O3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X-ray diffraction, differential thermal and thermo gravimetric analysis and transmission electron microscopy. It was found that the mechanochemical reaction process can be divided into two steps: the first step is the multi-phases mechanochemical reaction of lanthanum carbonate with NaOH to form amorphous lanthanum basic carbonate and lanthanum hydroxide, and the second step is the crystallization of basic lanthanum carbonate with the formula of La2(OH)2(CO3)2*H2O under a quasi-hydrothermal synthesis condition caused by the mechanical ball-milling. The synthesized La2O3 powder appears clearly separated spherical-like monodisperse nano-size particles in which particle size ranges from 30 to 50 nm.

  20. Ultra-Low-Temperature Reactions of Carbon Atoms with Hydrogen Molecules

    CERN Document Server

    Krasnokutski, S A; Renzler, M; Jäger, C; Henning, Th; Scheier, P


    The reactions of carbon atoms with dihydrogen have been investigated in liquid helium droplets at $T$ = 0.37 K. A calorimetric technique was applied to monitor the energy released in the reaction. The barrierless reaction between a single carbon atom and a single dihydrogen molecule was detected. Reactions between dihydrogen clusters and carbon atoms have been studied by high-resolution mass spectrometry. The formation of hydrocarbon cations of the type C$_m$H$_n^+$, with $m$ = 1-4 and $n$ = 1-15 was observed. With enhanced concentration of dihydrogen, the mass spectra demonstrated the main "magic" peak assigned to the CH$_5^+$ cation. A simple formation pathway and the high stability of this cation suggest its high abundance in the interstellar medium.

  1. Investigations on organogermanium compounds XII. Reactions of trialkylgermylalkalimetal compounds in hexamethylphosphoric triamide (HMPT) with some inorganic and organic compounds

    NARCIS (Netherlands)

    Bulten, E.J.; Noltes, J.G.


    Trialkylgermyl alkali metal compounds in HMPT have been found to be highly reactive nucleophiles. Reactions with some inorganic and organic compounds, such as oxygen, carbon dioxide, inorganic and orgaanic halides, aldehydes, ketones, epoxides and lactones are described. Several new carbon-functiona

  2. A Study on Reactions of Carbon-Carbonate Mixture at Elevated Temperature : As an Anode Media of SO-DCFC

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jun Ho; Kang, Kyungtae; Hwang, Jun Young [Korea Institute of Industrial Technoloy, Cheonan (Korea, Republic of)


    A direct carbon fuel cell (DCFC) generates electricity directly by converting the chemical energy in coal. In particular, a DCFC system with a solid oxide electrolyte and molten carbonate anode media has been proposed by SRI. In this system, however, there are conflicting effects of temperature, which enhances the ion conductivity of the solid electrolyte and reactivity at the electrodes while causing a stability problem for the anode media. In this study, the effect of temperature on the stability of a carbon-carbonate mixture was investigated experimentally. TGA analysis was conducted under either nitrogen or carbon dioxide ambient for Li{sub 2} CO{sub 3}, K{sub 2} CO{sub 3}, and their mixtures with carbon black. The composition of the exit gas was also monitored during temperature elevation. A simplified reaction model was suggested by considering the decomposition of carbonates and the catalyzed Boudouard reactions. The suggested model could well explain both the measured weight loss of the mixture and the gas formation from it.

  3. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions (United States)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.


    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  4. Application of Moessbauer Spectroscopy to the Carbon Oxides Hydrogenation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Cubeiro, M. L. [UCV, Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica (Venezuela, Bolivarian Republic of)], E-mail:; Gonzalez-Jimenez, F.; Goldwasser, M. R.; Perez-Zurita, M. J.; Pietri, E.; Garcia, L. [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, UCV (Venezuela, Bolivarian Republic of)


    Iron-based catalysts have favorable activity and selectivity properties for the CO and CO{sub 2} hydrogenation reactions. Several Fe phases (oxides and carbides) can be present in these catalysts. The interaction of Fe with the other components of the catalyst (support, promoters) can affect the ease of reduction and also its transformation during the reactions. In this work, the relationship between catalytic behavior in the CO and CO{sub 2} hydrogenation reactions and the Fe phase composition of fresh and reacted catalysts was studied. Two types of catalysts were tested: a laterite and the other one made of iron supported on alumina, both unpromoted and promoted with K and Mn. Only those Fe species which can be reduced-carburized, by means of a pretreatment or by an in situ transformation under the reaction, seem to be able to perform the CO or CO{sub 2} hydrogenation. The reoxidation of the Fe carbide to magnetite was not associated to deactivation. The selectivity seems to be more affected by Fe species difficult to reduce than by magnetite produced by reoxidation.

  5. Reaction Of Single-Wall Carbon Nanotubes With Radicals (United States)

    Lobach, A. S.; Solomentsev, V. V.; Obraztsova, E. D.; Shchegolikhin, A. N.; Sokolov, V. I.


    A method for functionalizing the sidewalls of HiPco SWNT via interaction with carbon- and metal-centered radicals is presented. A number of methods: UV-vis-NIR spectroscopy, thermogravimetric analysis, TEM and Raman spectroscopy provided a direct evidence of a chemical attachment of functional groups to the tubes. Functionalization was shown to be reversible: a thermal treatment led to the recovering of pristine structure of SWNT.

  6. Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

    Directory of Open Access Journals (Sweden)

    Xiaoqing Zhang


    Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

  7. Multiphase fluid-rock reactions among supercritical carbon dioxide, brine, aquifer, and caprock: relevance to geologic sequestration of carbon

    Energy Technology Data Exchange (ETDEWEB)

    Kaszuba, J. P. (John P.); Janecky, D. R. (David R.); Snow, M. G. (Marjorie G.)


    The reactive behavior of a multiphase fluid (supercritical CO{sub 2} and brine) under physical-chemical conditions relevant to geologic storage and sequestration in a carbon repository is largely unknown. Experiments were conducted in a flexible cell hydrothermal apparatus to evaluate multiphase fluid-rock (aquifer plus caprock) reactions that may impact repository integrity.

  8. Alkali promotion of N-2 dissociation over Ru(0001)

    DEFF Research Database (Denmark)

    Mortensen, Jens Jørgen; Hammer, Bjørk; Nørskov, Jens Kehlet


    Using self-consistent density functional calculations, we show that adsorbed Na and Cs lower the barrier for dissociation of N2 on Ru(0001). Since N2 dissociation is a crucial step in the ammonia synthesis reaction, we explain in this way the experimental observation that alkali metals promote...... the ammonia synthesis reaction over Ru catalysts. We also show that the origin of this effect is predominantly a direct electrostatic attraction between the adsorbed alkali atoms and the dissociating molecule....

  9. Reaction and surface characterization study of higher alcohol synthesis catalysts. 9: Pd- and alkali-promoted Zn/Cr-based spinels containing excess ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Minahan, D.M. [Union Carbide Corp., South Charleston, WV (United States); Epling, W.S.; Hoflund, G.B. [Univ. of Florida, Gainesville, FL (United States). Dept. of Chemical Engineering


    A Zn/Cr spinel support material was prepared which contains excess ZnO and then was promoted with 5.9 wt% Pd and varying amounts ranging from 0 to 7 wt % of either K or Cs. Each of these catalysts were tested at four different reactor operating conditions (T of 400 or 440 C and P of 1000 or 1500 psig) for higher alcohol synthesis (HAS) using a syngas feedstream (1:1 CO:H{sub 2}) after reductive pretreatment. High isobutanol production rates in conjunction with low methanol-to-isobutanol mole ratios ({le}1.0) and low hydrocarbon byproduct rates are desired. For the K-promoted catalysts the highest isobutanol production rates are obtained at the higher pressure and temperature settings of 1500 psig and 440 C, and methanol-to-isobutanol mole ratios below the ideal value of 1.0, which is required for downstream methyl tertiary-butyl ether (MTBE) synthesis, are obtained. The Cs-promoted catalysts generally yield higher isobutanol production rates than the K-promoted catalysts. The highest isobutanol production rate of 170 g/kg-h is obtained using the 3 wt% Cs-promoted catalyst at 1000 psig and 440 C. The lower pressure is economically advantageous with regard to process costs. Most importantly, this isobutanol production rate is quite high compared to others presented in the literature and demonstrates that Pd does enhance the synthesis of isobutanol. The catalytic activity remained stable over a 5-day test period for each catalyst. X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) were used to characterize these catalysts. The results obtained from these techniques indicate that pretreating the catalysts in 1 {times} 10{sup {minus}7} Torr of H{sub 2} at 300 C for 4 h causes an enrichment of the near-surface alkali-promotor concentration.

  10. Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Zhenhua Li; Pa Du


    The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.

  11. Reactions of carbon radicals generated by 1,5-transposition of reactive centers

    Directory of Open Access Journals (Sweden)



    Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

  12. Reaction of folic acid with single-walled carbon nanotubes (United States)

    Ellison, Mark D.; Chorney, Matthew


    The oxygen-containing functional groups on oxidized single-walled carbon nanotubes (SWNTs) are used to covalently bond folic acid molecules to the SWNTs. Infrared spectroscopy confirms intact molecular binding to the SWNTs through the formation of an amide bond between a carboxylic acid group on an SWNT and the primary amine group of folic acid. The folic acid-functionalized SWNTs are readily dispersible in water and phosphate-buffered saline, and the dispersions are stable for a period of two weeks or longer. These folic acid-functionalized SWNTs offer potential for use as biocompatible SWNTs.

  13. Investigation of thermochemistry associated with the carbon-carbon coupling reactions of furan and furfural using ab initio methods. (United States)

    Liu, Cong; Assary, Rajeev S; Curtiss, Larry A


    Upgrading furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan can be coupled with various C1 to C4 low molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase to produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (∼25 kcal/mol) are lower than the cellulose activation or decomposition reactions (∼50 kcal/mol). Cycloaddition of C5-C8 cyclo ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products, and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ∼20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.

  14. Surface reactions of molecular and atomic oxygen with carbon phosphide films. (United States)

    Gorham, Justin; Torres, Jessica; Wolfe, Glenn; d'Agostino, Alfred; Fairbrother, D Howard


    The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.

  15. Characterization of the major reactions during conversion of lignin to carbon fiber

    Directory of Open Access Journals (Sweden)

    Hendrik Mainka


    Full Text Available Lightweight design is an essential part of the overall Volkswagen strategy for reducing the CO2 emissions. The use of carbon fiber offers an enormous lightweight potential. In comparison to steel enabling a mass reduction of up to 70% in automotive parts without a degradation of the functionalities is possible. Today, the use of carbon fiber is limited in mass series applications of the automotive industry by the cost of the conventional C-fiber precursor polyacrylonitrile (PAN. 50% of the cost of a conventional carbon fiber already belongs to the cost of the PAN precursor. Lignin as a precursor for carbon fiber production can realize enormous savings in cost. For qualifying lignin-based carbon fiber for automotive mass production a detailed characterization of this new material is necessary. Therefore, nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy are used. Using the results of these experiments, the major reactions during conversion of lignin to carbon fiber are proposed.

  16. (abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary (United States)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S. K.


    The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

  17. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction (United States)

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


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

  18. Microstructural changes induced by CO2 exposure in alkali-activated slag/metakaolin pastes (United States)

    Bernal, Susan


    The structural changes induced by accelerated carbonation in alkali-activated slag/ metakaolin (MK) cements were determined. The specimens were carbonated for 540 h in an environmental chamber with a CO2 concentration of 1.0 ± 0.2%, a temperature of 20 ± 2ºC, and relative humidity of 65 ± 5 %. Accelerated carbonation led to decalcification of the main binding phase of these cements, which is an aluminium substituted calcium silicate hydrate (C-(N-)A-S-H) type gel, and the consequent formation of calcium carbonate. The sodium-rich carbonates trona (Na2CO3·NaHCO3·2H2O) and gaylussite (Na2Ca(CO3)2·5H2O) were identified in cements containing up to 10 wt.% MK as carbonation products. The formation of these carbonates is mainly associated with the chemical reaction between the CO2 and the free alkalis present in the pore solution. The structure of the carbonated cements is dominated by an aluminosilicate hydrate (N-A-S-H) type gel, independent of the MK content. The N-A-S-H type gels identified are likely to be derived both from the activation reaction of the MK, forming a low-calcium gel product which does not seem to undergo structural changes upon CO2 exposure, and the decalcification of C-(N-)A-S-H type gel. The carbonated pastes present a highly porous microstructure, more notable as the content of MK content in the cement increases, which might have a negative impact on the durability of these materials in service.

  19. Heterogeneously Catalysed Aldol Reactions in Supercritical Carbon Dioxide as Innovative and Non-Flammable Reaction Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai; Grunwaldt, Jan-Dierk


    hydrogenation of 2-butenal and is therefore a potential catalyst for the “one-pot” synthesis of 2-ethyl-2-hexenal and 2-ethylhexanal via combined hydrogenation and aldol reaction from 2-butenal. A number of characterisation techniques, such as temperature-programmed desorption of ammonia (NH3-TPD), transmission...

  20. Iron-carbon nanocomposite obtained by laser-induced gas-phase reactions (United States)

    Dumitrache, Florian V.; Morjan, Ion G.; Alexandrescu, Rodica; Rand, B.; Ciupina, Victor; Prodan, G.; Voicu, Ion N.; Sandu, Ioan C.; Soare, I.; Ploscaru, M.; Fleaca, C.; Brydson, R.; Vasile, Eugen


    Iron-carbon composite nanopowders have been synthesized by the CO2 laser pyrolysis of gas-phase reactants. The experimental device allows for a very low reaction time and a rapid freezing that creates nanoscale-condensed particles. Iron pentacarbonyl and ethylene-acetylene mixtures were used as iron and carbon precursors. In a two-steps experiment, the reaction products may present themselves as iron-based nanoparticles dispersed in a carbon matrix. By a careful control of experimental parameters and radiation geometries we demonstrate the feasibility of an efficient and well-controlled, single-step technique for the production of iron-based nano-cores embedded in carbon layers. Highly dispersed nanoparticles, narrow size distributions and particles with about 4.5 - 6 nm mean diameters were obtained. Electron microscopy and Raman spectroscopy were used in order to analyze the structure and composition of the obtained nanopowders as well as their Soxhlet residue.

  1. The Reaction of Carbonates in Contact with Superheated Silicate Melts: New Insights from MEMIN Laser Melting Experiments (United States)

    Hamann, C.; Hecht, L.; Schäffer, S.; Deutsch, A.; Lexow, B.


    The reaction of carbonates in contact with silicate impact melts is discussed quite controversially in the impact community. Here, we discuss four MEMIN laser melting experiments involving carbonates in contact with superheated silicate melts.

  2. Carbon nanotube inner phase chemistry: the Cl- exchange SN2 reaction. (United States)

    Halls, Mathew D; Raghavachari, Krishnan


    Density functional calculations have been carried out to investigate the nature of the inner phase of a (6,6) carbon nanotube, using the Cl(-) exchange S(N)2 reaction as an indicator. Inside the carbon nanotube the classical barrier height increases by 6.6 kcal/mol due to the nanotube polarizability. This suggests that the inner phase environment can be considered a form of solid solvation, offering the possibility of obtaining altered guest properties and reactivity through dielectric stabilization.

  3. Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions (United States)


    DOI: 10.1021/ct1000268. 26. A. J. Midey, T. M. Miller, A. A. Viggiano, N. C. Bera, S. Maeda, and K. Morokuma, Chemistry of VX Surrogates and Ion...THEORETICAL STUDIES OF GAS PHASE ELEMENTARY AND CARBON NANOSTRUCTURE GROWTH REACTIONS KEIJI MOROKUMA EMORY UNIVERSITY 09/19/2013 Final Report...Z39.18 30-09-2013 Final Performance Report 1 July 2010 - 30 June 2013 Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth

  4. Effect of reaction temperature on structure and fluorescence properties of nitrogen-doped carbon dots (United States)

    Zhang, Yi; Wang, Yaling; Feng, Xiaoting; Zhang, Feng; Yang, Yongzhen; Liu, Xuguang


    To investigate the effect of reaction temperature and nitrogen doping on the structure and fluorescence properties of carbon dots (CDs), six kinds of nitrogen-doped CDs (NCDs) were synthesized at reaction temperatures of 120, 140, 160, 180, 200 and 220 °C, separately, by using citric acid as carbon source and ammonia solution as nitrogen source. Nitrogen-free CDs (N-free CDs-180) was also prepared at 180 °C by using citric acid as the only carbon source for comparison. Results show that reaction temperature has obvious effect on carbonization degree, quantum yield (QY), ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) spectra but less effect on functional groups, nitrogen doping degree and fluorescence lifetime of NCDs. Compared with N-free CDs-180, NCDs-180 possesses enchanced QY and longer fluorescence lifetime. Doping nitrogen has obvious effect on UV-vis absorption and PL spectra but less effect on particles sizes and carbonization degree. The formation mechanism of NCDs is explored: QY of NCDs depends largely on the number of fluorescent polymer chains (FPC), the competition between FPC formation on the surface of NCDs and carbon core growth leads to the change in number of FPC, and consequently to the NCDs with highest QY at appropriate hydrothermal temperature.

  5. Impacts of diffusive transport on carbonate mineral formation from magnesium silicate-CO2-water reactions. (United States)

    Giammar, Daniel E; Wang, Fei; Guo, Bin; Surface, J Andrew; Peters, Catherine A; Conradi, Mark S; Hayes, Sophia E


    Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

  6. Synthesis of Diethyl Oxalate by a Coupling—Regeneration Reaction of Carbon Monoxide

    Institute of Scientific and Technical Information of China (English)

    FandongMeng; GenhuiXu; 等


    This article describes a process for the synthesis of diethyl oxalate by a copling reaction of carbon monoxide,catalyzed by palladium in the presence of ethyl nitrite ,The kinetics and mechanism of the coupling and regeneration reaction are also discussed ,This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.

  7. Pair natural orbital and canonical coupled cluster reaction enthalpies involving light to heavy alkali and alkaline earth metals: the importance of sub-valence correlation

    KAUST Repository

    Minenkov, Yury


    In this work, we tested canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) for a set of 32 ligand exchange and association/dissociation reaction enthalpies involving ionic complexes of Li, Be, Na, Mg, Ca, Sr, Ba and Pb(ii). Two strategies were investigated: in the former, only valence electrons were included in the correlation treatment, giving rise to the computationally very efficient FC (frozen core) approach; in the latter, all non-ECP electrons were included in the correlation treatment, giving rise to the AE (all electron) approach. Apart from reactions involving Li and Be, the FC approach resulted in non-homogeneous performance. The FC approach leads to very small errors (<2 kcal mol-1) for some reactions of Na, Mg, Ca, Sr, Ba and Pb, while for a few reactions of Ca and Ba deviations up to 40 kcal mol-1 have been obtained. Large errors are both due to artificial mixing of the core (sub-valence) orbitals of metals and the valence orbitals of oxygen and halogens in the molecular orbitals treated as core, and due to neglecting core-core and core-valence correlation effects. These large errors are reduced to a few kcal mol-1 if the AE approach is used or the sub-valence orbitals of metals are included in the correlation treatment. On the technical side, the CCSD(T) and DLPNO-CCSD(T) results differ by a fraction of kcal mol-1, indicating the latter method as the perfect choice when the CPU efficiency is essential. For completely black-box applications, as requested in catalysis or thermochemical calculations, we recommend the DLPNO-CCSD(T) method with all electrons that are not covered by effective core potentials included in the correlation treatment and correlation-consistent polarized core valence basis sets of cc-pwCVQZ(-PP) quality.

  8. Initial reaction between CaO and SO2 under carbonating and non-carbonating conditions

    DEFF Research Database (Denmark)

    Rasmussen, Martin Hagsted; Wedel, Stig; Pedersen, Kim H.;


    The initial kinetics of the CaO/SO2 reaction have been investigated for reaction times shorter than 1s and in the temperature interval between 450 and 600°C under both carbonating and non-carbonating conditions (0-20 vol% CO2) to clarify how recirculating CaO influences the emission of SO2 from...... showed that the CaO conversion with respect to SO2 declined when the CO2 concentration was increased. Under all conditions, larger specific surface areas of CaO gave higher reaction rates with SO2. Higher temperatures had a positive effect on the reaction between SO2 and CaO under non...... a modern dry kiln preheater system for cement production. Calcined Faxe Bryozo limestone with a particle size smaller than 400μm was utilized as CaO source. It was shown, both theoretically and experimentally, that the observed reaction rates were influenced by mass transport limitations. The results...

  9. Inlfuence of the Alkali Treatment of HZSM-5 Zeolite on Catalytic Performance of PtSn-Based Catalyst for Propane Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    Huang Li; Zhou Shijian; Zhou Yuming; Zhang Yiwei; Xu Jun; Wang Li


    The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2-physisorption, and NH3-TPD analysis. The results showed that the alkali treatment can modify the physicochemical prop-erties of HZSM-5 zeolite. In this case, the porous material ATZ showed larger external surface area with less acid sites as compared to the HZSM-5 zeolite. It was found out that the alkali treatment of HZSM-5 zeolite could promote the catalytic performance of PtSn/ATZ catalyst. The possible reason was ascribed to the low acidity of ATZ. Furthermore, the presence of mesopores could reduce the carbon deposits on the metallic surface, which was also favorable for the dehydrogenation reaction.


    DEFF Research Database (Denmark)


    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...


    Energy Technology Data Exchange (ETDEWEB)

    M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter


    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation, before and/or during carbonation, may provide an important parameter for enhancing carbonation reaction processes. Mg(OH){sub 2} was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (1) its structural and chemical simplicity, (2) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (3) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO{sub 2} sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for minimizing the cost of any lamellar-hydroxide-based mineral carbonation sequestration process. This final report covers the overall progress of this grant.

  12. Structure and Reactions of Carbon and Hydrogen on Ru(0001): A Scanning Tunneling Microscopy Study

    Energy Technology Data Exchange (ETDEWEB)

    Shimizu, Tomoko K.; Mugarza, Aitor; Cerda, Jorge; Salmeron, Miquel


    The interaction between carbon and hydrogen atoms on a Ru(0001) surface was studied using scanning tunneling microscopy (STM), Density Functional Theory (DFT) and STM image calculations. Formation of CH species by reaction between adsorbed H and C was observed to occur readily at 100 K. When the coverage of H increased new complexes of the form CH+nH (n = 1, 2 and 3) were observed. These complexes, never observed before, might be precursors for further hydrogenation reactions. DFT analysis reveals that a considerable energy barrier exists for the CH+H {yields} CH{sub 2} reaction.

  13. N, S co-doped carbon dots with orange luminescence synthesized through polymerization and carbonization reaction of amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Ya-Wen [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Ma, De-Kun, E-mail: [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Wang, Wei; Chen, Jing-Jing; Zhou, Lin; Zheng, Yi-Zhou [Department of Hematology, The First Affiliated Hospital of Wenzhou Medical University, Wenzhou, Zhejiang 325027 (China); Yu, Kang, E-mail: [Department of Hematology, The First Affiliated Hospital of Wenzhou Medical University, Wenzhou, Zhejiang 325027 (China); Huang, Shao-Ming, E-mail: [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China)


    Graphical abstract: N, S co-doped CDs with orange luminescence were synthesized through one-pot polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. - Highlights: • N, S co-doped CDs were synthesized by one-pot carbonization reactions, using two different amino acids as raw materials. • The as-obtained N, S co-doped CDs showed unique orange fluorescence under excitation at room temperature. • The products could be applied in the imaging of peritoneal macrophages of mice without any functionalization. - Abstract: For practical application, it is highly desirable to obtain carbon dots (CDs) through environmentally benign synthetic route, using green raw materials. On the other hand, at present, most of CDs reported in the literature showed blue, green and yellow emission. Therefore it is still necessary to develop new strategy to obtain CDs with longer wavelength emission in order to expand their application range. Toward this end, in this study, N, S co-doped CDs were synthesized through one-pot condensation polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. Taking the reaction of L-serine with L-cystine as an example, the as-obtained products were characterized by various techniques such as transmission electron microscopy, elemental analysis, Fourier-transform infrared spectrum, X-ray photoelectron spectra, and so on. Interestingly, N, S co-doped CDs displayed unique orange emission at room temperature. The possible photoluminescence mechanism of N, S co-doped CDs was proposed. Furthermore, the as-synthesized N, S co-doped CDs were directly applied in the imaging of peritoneal macrophages of mice.

  14. Oxalyl chloride as a practical carbon monoxide source for carbonylation reactions

    DEFF Research Database (Denmark)

    Hansen, Steffen V F; Ulven, Trond


    A method for generation of high-quality carbon monoxide by decomposition of oxalyl chloride in an aqueous hydroxide solution is described. The usefulness of the method is demonstrated in the synthesis of heterocycles and for hydroxy-, alkoxy-, amino-, and reductive carbonylation reactions, in sev...

  15. Carbophilic versus thiophilic attack in the reaction of metallated aromates and heteroaromates with carbon disulfide

    NARCIS (Netherlands)

    Verkruijsse, H.D.; Brandsma, L.


    Copper(I) halides catalyse the formation of carbodithioates RCSSLi in the reaction of aryl- or heteroaryl-lithium reagents with carbon disulfide. Subsequent addition of methyl iodide gives the dithioesters RCSSCH3 in high yields. Appreciable amounts of the methyl sulfides RSCH3 and tars are obtained

  16. Direct Electrochemical Reaction of Horseradish Peroxidase Immobilized on the Surface of Active Carbon Powders

    Institute of Scientific and Technical Information of China (English)

    Dong Mei SUN; Chen Xin CAI; Wei XING; Tian Hong LU


    It is reported for the first time that horseradish peroxidase(HRP)immobilized on the active carbon can undergo a direct quasi-reversible electrochemical reaction. In addition,the immobilized HRP showed the stable bioelectrocatalytic activity for the reduction of H2O2.

  17. Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results (United States)

    Rosenbauer, Robert J.; Thomas, Burt; Bischoff, James L.; Palandri, James


    Basaltic rocks are potential repositories for sequestering carbon dioxide (CO2) because of their capacity for trapping CO2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO2-charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO2, an average basaltic MgO content of 8% is equivalent to 2.6 × 108 metric ton CO2/km3 basalt.

  18. Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

    Energy Technology Data Exchange (ETDEWEB)

    Penner, Larry R.; O' Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.


    Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism.

  19. Heterogeneous reactions of gaseous methanesulfonic acid with calcium carbonate and kaolinite particles

    Institute of Scientific and Technical Information of China (English)


    Heterogeneous reactions of gaseous methanesulfonic acid (MSA) with calcium carbonate (CaCO3) and kaolinite particles at room temperature were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatography (IC).Methanesulfonate (MS-) was identified as the product in the condensed phase,in accordance with the product of the reaction of gaseous MSA with NaCl and sea salt particles.When the concentration of gaseous MSA was 1.34 × 10-13 molecules cm-3,the uptake coefficient was (1.21 ± 0.06) × 10-8 (1) for the reaction of gaseous MSA with CaCO3 and (4.10 ± 0.65) × 10 10 (1) for the reaction with kaolinite.Both uptake coefficients were significantly smaller than those of the reactions of gaseous MSA with NaCl and sea salt particles.

  20. Structural evaluation of a prestressed concrete bridge under an alkali-silica reaction; Evaluacion estructural de un puente de hormigon pretensado afectado por una reaccion alcali-silice

    Energy Technology Data Exchange (ETDEWEB)

    Carpintero Garcia, I.; Bermudez Adriozola, B.


    The Central Laboratory of Structures and Materials (CEDEX) was commissioned by the National Department of Highways to evaluate the safety conditions of one bridge built on 1997, which is part of the net of the Spanish National Highways. Even at the first inspection many cracks were detected in the concrete deck, associated with expansion concrete processes. This examination revealed that concrete deterioration was not associated with any reinforcement corrosion process; in fact, there were no symptoms of this pathology all along the bridge. for that reason the internal chemical reactions were considered as the most probable cause for the expansion of concrete, as no symptoms of deterioration due to external attack were found. In order to check the origin of concrete expansion, some tests were carried out on concrete samples drilled on the decks. Results of these tests show that there had been internal reactions in concrete mass which explains its expansion and the appearance of those cracks observed. Further more, some other activities were also carried out on site to estimate the importance of the structural damages, as topographic levelling and dynamic testing of the decks. Also the mechanical properties of concrete probes were tested at laboratory. This article shows the main results obtained on the study carried on to determine the cause and significance of the structural damages of the bridge. (Author) 3 refs.

  1. Convert Graphene Sheets to Boron Nitride and Boron Nitride-Carbon Sheets via a Carbon-Substitution-Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Han, W.; Yu, H.-G.; Liu. Z.


    Here we discuss our synthesis of highly crystalline pure boron nitride (BN) and BN-carbon (BN-C) sheets by using graphene sheets as templates via a carbon-substitution reaction. Typically, these sheets are several micrometers wide and have a few layers. The composition ratios of BN-C sheets can be controlled by the post-treatment (remove carbon by oxidation) temperature. We also observed pure BN and BN-C nanoribbons. We characterized the BN-C sheets via Raman spectroscopy and density functional theory calculations. The results reveal that BN-C sheets with an armchair C-BN chain, and embedded C{sub 2} or C{sub 6} units in BN-dominated regions energetically are the most favorable.

  2. Carbon nanohybrids used as catalysts and emulsifiers for reactions in biphasic aqueous/organic systems

    Institute of Scientific and Technical Information of China (English)

    Daniel E. Resasco


    This mini-review summarizes some novel aspects of reactions conducted in aqueous/organic emul-sions stabilized by carbon nanohybrids functionalized with catalytic species. Carbon nanohybrids represent a family of solid catalysts that not only can stabilize water-oil emulsions in the same fash-ion as Pickering emulsions, but also catalyze reactions at the liquid/liquid interface. Several exam-ples are discussed in this mini-review. They include (a) aldol condensation-hydrodeoxygenation tandem reactions catalyzed by basic (MgO) and metal (Pd) catalysts, respectively; (b) Fischer-Tropsch synthesis catalyzed by carbon-nanotube-supported Ru;and (c) emulsion polymerization of styrene for the production of conductive polymer composites. Conducting these reactions in emul-sion generates important advantages, such as increased liquid/liquid interfacial area that conse-quently means faster mass transfer rates of molecules between the two phases, effective separation of products from the reaction mixture by differences in the water-oil solubility, and significant changes in product selectivity that can be adjusted by modifying the emulsion characteristics.

  3. Reactions of the Carbon Anode in Alternative Battery and Fuel Cell Configurations

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, J F; Krueger, R


    A model is formulated by combining carbonate dissociation with pre-existing anode mechanisms involving heterogeneous reaction kinetics. The proposed model accounts for both the observed preponderance of CO{sub 2} evolution and dependence of rate on carbon anode microstructure. Implications of the model for the design of carbon batteries and fuel cells are discussed, and the laboratory cells used in earlier research are described. High coulombic efficiencies for the net reaction C + O{sub 2} = CO{sub 2} require severely limiting the thickness of paste anodes in powder-fed fuel cells while the unreacting surfaces of solid prismatic anodes must be isolated from the CO{sub 2} product atmosphere to prevent Boudouard corrosion, according to C + CO{sub 2} = 2CO.

  4. Estudo das reações alcalis-sílica associadas ao uso da lama vermelha em argamassas colantes e de revestimento Study of alkali-silica reactions associated with the use of red mud in plastering mortars

    Directory of Open Access Journals (Sweden)

    D. V. Ribeiro


    Full Text Available A incorporação de resíduos industriais em matrizes cimentícias, com o objetivo de inertização, é uma alternativa de reutilização que tem sido bastante estudada nos últimos anos. No presente trabalho, estudou-se a lama vermelha, resíduo sólido gerado no processo de beneficiamento da bauxita e que, devido a seu elevado pH, é considerado "perigoso". Apesar do uso deste resíduo ter sido reportada em trabalhos anteriores, algumas patologias podem estar associadas à sua utilização, devido à elevada concentração de íons alcalinos (principalmente o sódio, favorecendo as reações álcalis-sílica (RAS e às dificuldades de moldagem (reologia devido à elevada finura deste resíduo. Apesar destes prováveis problemas provenientes do uso indiscriminado da lama vermelha como adição às argamassas e concretos, ainda são poucas as pesquisas que os contemplam, sendo este o foco do presente trabalho. Foram verificadas as propriedades reológicas das argamassas, utilizando um reômetro e a avaliação da RAS, de acordo com as normas ASTM C 1260-07 e NBR 11582. Os resultados obtidos foram bastante satisfatórios quanto ao comportamento das argamassas frente à RAS, apesar da elevada concentração de álcalis na lama vermelha, com grande influência reológica.The incorporation of industrial wastes in cementitious matrices, with the goal of inertization, is an alternative of reuse that has been extensively studied in recent years. In this paper, the red mud, the main waste generated in aluminum and alumina production by the Bayer process from bauxite ore and considered "hazardous" due to the high pH, was studied. Despite the use of this waste have been reported in previous studies, some pathologies may be associated with its use, due to high concentration of alkali ions (mainly sodium, favoring the alkali-silica reactions (ASR and the difficulties of molding (rheology because of high fineness of this waste. Despite these potential

  5. Infrared Photodissociation Spectroscopy of Vanadium-Carbon Dioxide Cations: Evidence for AN Intracluster Reaction. (United States)

    Brathwaite, Antonio D.; Ricks, Allen M.; Duncan, Michael A.


    Cationic vanadium-carbon dioxide clusters, consisting of up to ten carbon dioxide ligands, are produced in a molecular beam via laser vaporization in a pulsed nozzle source. The cations are mass selected and studied via infrared photodissociation spectroscopy in the 600-4000 cm1 region. The number of infrared active bands, their frequency positions and their relative intensities, allows us to gain insight into the structure and bonding of these species. The sudden appearance of new infrared bands in the spectra of complexes having seven or more ligands provides evidence for an intracluster reaction. We explore possible reaction products by comparing these spectra to those of vanadium and vanadium oxide-carbonyls. Low frequency measurements and DFT calculations have allowed us to identify complexes containing a metal atom bonded to an oxalate-like structure as the product of these reactions.

  6. Catalytic Asymmetric Carbon-Carbon Forming Reactions Catalyzed Chiral Schiff Base-Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Takanori; Tanaka; Masahiko; Hayashi


    1 Results In 1991, we disclosed the novel asymmetric catalysts prepared from chiral Schiff base and titanium alkoxide in the reaction of asymmetric silylcyanation of aldehydes (eq.1)[1]. Since our first report, chiral Schiff base-metal complex was proven to be efficient in a variety of asymmetric reactions. We reported the first example of enantioselective addition of diketene to aldehydes promoted by chiral Schiff base-titanium alkoxide complexes (eq.2)[2]. The products of this reaction have been cove...

  7. Application of supported alkali catalysts in Prins reaction%负载碱催化剂在Prins反应中的应用

    Institute of Scientific and Technical Information of China (English)

    王海永; 吕慧; 林晨; 朱振炜; 许康栋; 曹贵平


    Solid base catalysts MnO/Al2O3 (M=Na, K, Cs, Mg, Ca, Sr,n=1 or 2) prepared by impregnation method and C-Cs2O/Al2O3 by co-precipitation method were applied in Prins reaction. Their base amount and pKa in water were determined. The structure and physico-chemical properties of the carrier and prepared catalysts were characterized by CO2-TPD, X-ray diffraction, and nitrogen adsorption. The performance of catalysts was evaluated by condensation reaction of isobutene with paraformaldehyde to produce 3-methyl-3-buten-1-ol. The results showed that the performance of catalysts related directly with their basic property and structure. The C-Cs2O/Al2O3 catalyst had stronger basicity and showed superior catalytic performance, and the conversion of formaldehyde and selectivity to MBO reached up to 100.0% and 86.0% respectively. The mechanism of Prins reaction over solid base catalyst was also discussed. The base sites could active theα-H of isobutene, and so could promote the Prins reaction.%分别采用浸渍法和共沉淀法制备了负载金属氧化物的固体碱催化剂MnO/Al2O3(M=Na,K,Cs,Mg,Ca, Sr;n=1,2)和C-Cs2O/Al2O3,测定了催化剂的碱量和pKa值,分别采用CO2-TPD、X射线衍射、N2物理吸附表征了催化剂的物理化学性质。以异丁烯与多聚甲醛经Prins反应制备3-甲基-3-丁烯-1-醇(MBO)为体系考察催化剂活性。结果表明,催化剂的碱性和结构直接影响其催化活性,采用共沉淀法制备的Cs2O/Al2O3催化剂具有更强的碱性,表现出了优越的反应活性,甲醛的转化率和产物MBO的选择性分别为100.0%和86.0%。探讨了固体碱催化反应的机理,发现碱性位可以活化异丁烯的α-H,促进Prins反应。

  8. Proton transfer reactions in carbon nanotubes endohedrally functionalized with selected polar amino acid sidechains

    Energy Technology Data Exchange (ETDEWEB)

    Abi, T.G. [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India); Taraphder, Srabani, E-mail: [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India)


    Graphical abstract: Free Energies of activation and reaction for intramolecular proton transfer between polar amino acid sidechains and hydroxyl groups inside the core of endohedrally functionalized single walled carbon nanotubes. Highlights: Black-Right-Pointing-Pointer EVB based free energy simulation of proton transfer in hydrophobic confinement. Black-Right-Pointing-Pointer Aminoacid sidechain and OH group suspended within carbon nanotube act as reactants. Black-Right-Pointing-Pointer Donors like His and Glu are efficient in confinement aided by local hydrogen bonds. -- Abstract: We use the empirical-valence-bond (EVB) theory to investigate intramolecular proton transfer reactions between a selected set of polar amino acid sidechains and hydroxyl groups suspended inside carbon nanotubes to model the effect of hydrophobic confinement on the energetics of proton transfer involving (i) translocation of an excess protonic charge (with protonated histidine sidechain as donor) and (ii) transformation of a neutral reactant state to a charge-separated product state (with sidechains of Asp, Glu, Ser and Thr as donor). In both the cases, confinement in hydrophobic medium is found to change the associated free energies compared to their respective values in the bulk solution phase. Presence of stable hydrogen bonding within the pore is found to have a significant effect on both free energies of reaction and activation and thus governs the thermodynamic and kinetic feasibilities of these intramolecular reactions in hydrophobic confinement.

  9. Pyrolysis characteristic of kenaf studied with separated tissues, alkali pulp, and alkali li

    Directory of Open Access Journals (Sweden)

    Yasuo Kojima


    Full Text Available To estimate the potential of kenaf as a new biomass source, analytical pyrolysis was performed using various kenaf tissues, i.e., alkali lignin and alkali pulp. The distribution of the pyrolysis products from the whole kenaf was similar to that obtained from hardwood, with syringol, 4-vinylsyringol, guaiacol, and 4-vinylguaiacol as the major products. The phenols content in the pyrolysate from the kenaf core was higher than that from the kenaf cuticle, reflecting the higher lignin content of the kenaf core. The ratios of the syringyl and guaiacyl compounds in the pyrolysates from the core and cuticle samples were 2.79 and 6.83, respectively. Levoglucosan was the major pyrolysis product obtained from the kenaf alkali pulp, although glycol aldehyde and acetol were also produced in high yields, as previously observed for other cellulosic materials. Moreover, the pathways for the formation of the major pyrolysis products from alkali lignin and alkali pulp were also described, and new pyrolysis pathways for carbohydrates have been proposed herein. The end groups of carbohydrates bearing hemiacetal groups were subjected to ring opening and then they underwent further reactions, including further thermal degradation or ring reclosing. Variation of the ring-closing position resulted in the production of different compounds, such as furans, furanones, and cyclopentenones.

  10. Enhance luminescence by introducing alkali metal ions (R+ = Li+, Na+ and K+) in SrAl2O4:Eu3+ phosphor by solid-state reaction method (United States)

    Prasad Sahu, Ishwar


    In the present article, the role of charge compensator ions (R+ = Li+, Na+ and K+) in europium-doped strontium aluminate (SrAl2O4:Eu3+) phosphors was synthesized by the high-temperature, solid-state reaction method. The crystal structures of sintered phosphors were in a monoclinic phase with space group P21. The trap parameters which are mainly activation energy (E), frequency factor (s) and order of the kinetics (b) were evaluated by using the peak shape method. The calculated trap depths are in the range from 0.76 to 0.84 eV. Photoluminescence measurements showed that the phosphor exhibited emission peak with good intensity at 595 nm, corresponding to 5D0-7F1 (514 nm) orange emission and weak 5D0-7F2 (614 nm) red emission. The excitation spectra monitored at 595 nm show a broad band from 220 to 320 nm ascribed to O-Eu charge-transfer state transition and the other peaks in the range of 350-500 nm originated from f-f transitions of Eu3+ ions. The strongest band at 394 nm can be assigned to 7F0-5L6 transition of Eu3+ ions due to the typical f-f transitions within Eu3+ of 4f6 configuration. The latter lies in near ultraviolet (350-500 nm) emission of UV LED. CIE color chromaticity diagram and thermoluminescence spectra confirm that the synthesized phosphors would emit an orange-red color. Incorporating R+ = Li+, Na+ and K+ as the compensator charge, the emission intensity of SrAl2O4:Eu3+ phosphor can be obviously enhanced and the emission intensity of SrAl2O4:Eu3+ doping Li+ is higher than that of Na+ or K+ ions.

  11. CaCO3, its reaction and carbonate rocks: terahertz spectroscopy investigation (United States)

    Zhan, Honglei; Wu, Shixiang; Zhao, Kun; Bao, Rima; Xiao, Lizhi


    Carbonate-rich rocks cover a primary part of the earth’s petroleum geology reservoir. The study of carbonate has special significance and more effective study methods are now needed. In order to improve the availability of carbonate rock detection, terahertz (THz) spectroscopy was employed to investigate relevant materials in Na2CO3  +  CaCl2  =  CaCO3  +  2NaCl, which is often used to generate CaCO3. By comparing the materials composited with different ions, it can be revealed that Ca2+, \\text{CO}32- , Na+ and Cl- have respective absorption features at different frequencies. Furthermore, by utilizing a conservation equation it can be observed that the average refractive indices of Na2CO3 as well as CaCl2 equal those of CaCO3 and NaCl in the entire range. Combining the absorption and refractive effect of the materials in the reaction can comprehensively characterize the different substances and reveal the inner interaction during the reaction. THz spectra can deduce the process of molecule rearrangement in the chemical reaction of long-term rock evolution. Besides, the absorption features of the real carbonate rock collected from the nearest town of Sinan county, Guizhou province in Yunnan-Guizhou plateau validate the peaks’ central frequencies of ions and the principal components of carbonates, which can be in agreement with the SEM-EDS analysis. This research will supply a spectral tool to identify the particles in the rock and deduce an evolution of petroleum carbonate reservoir.

  12. Sulfur reactions and cryptic cross-linkages to oxygen, iron, and carbon cyclin (United States)

    Druschel, G.; Kafantaris, F. C. A.; Fike, D. A.; Schmitt-Kopplin, P.; Dvorski, S.; Oduro, H.


    Sulfur speciation in any setting is controlled by a complex series of redox reactions, polymerization, and complexation reactions that are affected by both biotic and abiotic processes. Additionally there are several crossroads of reactions with oxygen, carbon, and iron in which polysulfide molecules serve as a key reaction component that affects not only sulfur speciation, but the speciation, solubility, and bioavailability of these elements as well. Utilizing a combination of analytical approaches including electrochemistry, spectroscopy, mass spectrometry, and chromatography, we have started to unravel the interconnections between sulfur and other key elements, and how microorganisms may be either direct or indirect contributors to these chemical and mineralogical signatures. In microbial mats, we have observed microbial production of significant hydrogen peroxide under UV-stressed conditions. This peroxide interaction with hydrogen sulfide changes the kinetics and the pathways of abiotic sulfur reactions, potentially affecting the overall bioavailability and isotopic fractionations for specific reactions via a change in the linkage between oxygen and sulfur cycling. In systems containing significant iron, we have observed the production of an electroactive form of ferrous iron and sulfide (FeS(aq)) that is of a size that can be described between a dissolved molecular cluster and a small nanoparticle. This FeS(aq) can be a significant fraction of the dissolved iron or sulfide in a system, and is a key part of both the solubility of iron and sulfur and the pathways potentially important for pyritization reactions. In systems where we investigate the links between sulfur and carbon, laboratory and field experiments indicate a wide range of large and more reduced organic compounds are highly reactive towards polysulfide. Utilizing Fourier-transform ion cyclotron resonance mass spectrometry in conjunction with electrochemistry and chromatography, we are seeing a

  13. Synthesis of graphitic carbon nitride through pyrolysis of melamine and its electrocatalysis for oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    He-Sheng Zhai; Lei Cao; Xing-Hua Xia


    Graphitic carbon nitride (g-C3N4) was synthesized via direct pyrolysis of melamine and its electrocatalysis toward oxygen reduction reaction was studied.The morphology and structures of the products were characterized by scanning electron microscope and X-ray powder diffractometer.It was found that higher pyrolysis temperature resulted in more perfect crystalline structure of the graphitic carbon nitride product.Electrochemical characterizations show that the g-C3N4 has electrocatalytic activity toward ORR through a two-step and two-electron process.

  14. Synthesis of N-rich microporous carbon materials from chitosan by alkali activation using Na{sub 2}CO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Ilnicka, Anna; Lukaszewicz, Jerzy P., E-mail:


    Highlights: • The novel manufacturing procedure of nitrogen-rich carbon materials. • The biopolymer chitosan can be activated by sodium carbonate. • The effect of the addition of activator and the temperature of carbonization was investigated. • The N-rich carbon materials exhibit high specific surface area and microporous structure. - Abstract: The paper presents the first systematic study on the synthesis of nitrogen-rich nanoporous activated carbons by chitosan carbonization in the presence of a hard template (activator), i.e. Na{sub 2}CO{sub 3}. Carbonization process was carried out in the range of 600–900 °C under a flow of nitrogen. The effect of the addition of different volumes of activator and the temperature of carbonization on the development of specific surface area and pore structure (pore volume and median pore diameter) of the activated carbons was investigated. Additionally, the nitrogen content and nitrogen-containing surface species were determined by means of XPS and combustion elemental analysis. The nitrogen content was placed in the range of 2.4–13.1 wt.%. On the grounds of the low-temperature adsorption of nitrogen, it was found that obtained adsorption isotherms were of type-I, based on the IUPAC classification, which is typical for microporous materials.

  15. Alkali-activated cementitious materials: Mechanisms, microstructure and properties (United States)

    Jiang, Weimin

    The goal of this study was to examine the activation reaction, microstructure, properties, identify the mechanisms of activation, and achieve an enhanced understanding of activation processes occurring during the synthesis of alkali activated cementitious materials (AAC). The discussions classify the following categories. (1) alkali activated slag cement; (2) alkali activated portland-slag cement; (3) alkali activated fly ash-slag cement; (4) alkali activated pozzolana-lime cement; (5) alkali activated pozzolana cement. The activators involved are NaOH, KOH; Nasb2SOsb4;\\ Nasb2COsb3;\\ CaSOsb4, and soluble silicate of sodium and potassium. The effect of alkali activation on the microstructure of these materials were analyzed at the micro-nanometer scale by SEM, EDS, ESEM, and TEM. Also sp{29}Si and sp{27}Al MAS-NMR, IR, Raman, TGA, and DTA were performed to characterize the phase in these systems. Slag, fly ash, silica fume, as well as blended cements containing mixtures of these and other components were characterized. A set of ordinary portland cement paste samples served as a control. This study confirmed that AAC materials have great potential because they could generate very early high strength, greater durability and high performance. Among the benefits to be derived from this research is a better understanding of the factors that control concrete properties when using AAC materials, and by controlling the chemistry and processing to produce desired microstructures and properties, as well as their durability.

  16. Free-standing and mechanically flexible mats consisting of electrospun carbon nanofibers made from a natural product of alkali lignin as binder-free electrodes for high-performance supercapacitors (United States)

    Lai, Chuilin; Zhou, Zhengping; Zhang, Lifeng; Wang, Xiaoxu; Zhou, Qixin; Zhao, Yong; Wang, Yechun; Wu, Xiang-Fa; Zhu, Zhengtao; Fong, Hao


    Mechanically flexible mats consisting of electrospun carbon nanofibers (ECNFs) were prepared by first electrospinning aqueous mixtures containing a natural product of alkali lignin together with polyvinyl alcohol (PVA) into composite nanofiber mats followed by stabilization in air and carbonization in an inert environment. Morphological and structural properties, as well as specific surface area, total pore volume, average pore size, and pore size distribution, of the lignin-based ECNF mats were characterized; and their electrochemical performances (i.e., capacitive behaviors) were evaluated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The lignin-based ECNF mats exhibited outstanding performance as free-standing and/or binder-free electrodes of supercapacitors. For example, the ECNFs made from the composite nanofibers with mass ratio of lignin/PVA being 70/30 (i.e., ECNFs (70/30)) had the average diameter of ∼100 nm and the Brunauer-Emmett-Teller (BET) specific surface area of ∼583 m2 g-1. The gravimetric capacitance of ECNFs (70/30) electrode in 6 M KOH aqueous electrolyte exhibited 64 F g-1 at current density of 400 mA g-1 and 50 F g-1 at 2000 mA g-1. The ECNFs (70/30) electrode also exhibited excellent cycling durability/stability, and the gravimetric capacitance merely reduced by ∼10% after 6000 cycles of charge/discharge.

  17. An Alternative Method for Generating Arynes from ortho-Silylaryl Triflates: Activation by Cesium Carbonate in the Presence of a Crown Ether

    Directory of Open Access Journals (Sweden)

    Suguru Yoshida


    Full Text Available An alternative method for generating arynes from ortho-silylaryl triflates using cesium carbonate and 18-crown-6 is reported. The method was efficiently applied to a variety of reactions between several arynes and arynophiles. We also demonstrated that the efficiency of aryne generation is significantly affected by the alkali metal countercation of the carbonate.

  18. [Involvement of carbonate/bicarbonate ions in the superoxide-generating reaction of adrenaline autoxidation]. (United States)

    Sirota, T V


    An important role of carbonate/bicarbonate ions has been recognized in the superoxide generating reaction of adrenaline autooxidation in an alkaline buffer (a model of quinoid adrenaline oxidation in the body). It is suggested that these ions are directly involved not only in formation of superoxide anion radical (О(2)(-)) but also other radicals derived from the carbonate/bicarbonate buffer. Using various buffers it was shown that the rate of accumulation of adrenochrome, the end product of adrenaline oxidation, and the rate of О(2)(-)· formation depend on concentration of carbonate/bicarbonate ions in the buffer and that these ions significantly accelerate adrenaline autooxidation thus demonstrating prooxidant properties. The detectable amount of diformazan, the product of nitro blue tetrazolium (NBT) reduction, was significantly higher than the amount of adrenochrome formed; taking into consideration the literature data on О(2)(-)· detection by NBT it is suggested that adrenaline autooxidation is accompanied by one-electron reduction not only of oxygen dissolved in the buffer and responsible for superoxide formation but possible carbon dioxide also dissolved in the buffer as well as carbonate/bicarbonate buffer components leading to formation of corresponding radicals. The plots of the dependence of the inhibition of adrenochrome and diformazan formation on the superoxide dismutase concentration have shown that not only superoxide radicals are formed during adrenaline autooxidation. Since carbonate/bicarbonate ions are known to be universally present in the living nature, their involvement in free radical processes proceeding in the organism is discussed.

  19. Nitrogen-Doped Carbon Nanotube and Graphene Materials for Oxygen Reduction Reactions

    Directory of Open Access Journals (Sweden)

    Qiliang Wei


    Full Text Available Nitrogen-doped carbon materials, including nitrogen-doped carbon nanotubes (NCNTs and nitrogen-doped graphene (NG, have attracted increasing attention for oxygen reduction reaction (ORR in metal-air batteries and fuel cell applications, due to their optimal properties including excellent electronic conductivity, 4e− transfer and superb mechanical properties. Here, the recent progress of NCNTs- and NG-based catalysts for ORR is reviewed. Firstly, the general preparation routes of these two N-doped carbon-allotropes are introduced briefly, and then a special emphasis is placed on the developments of both NCNTs and NG as promising metal-free catalysts and/or catalyst support materials for ORR. All these efficient ORR electrocatalysts feature a low cost, high durability and excellent performance, and are thus the key factors in accelerating the widespread commercialization of metal-air battery and fuel cell technologies.

  20. Cycloaddition Reaction of Carbon Dioxide to Epoxides Catalyzed by Polymer-Supported Quaternary Phosphonium Salts

    Directory of Open Access Journals (Sweden)

    Yubing Xiong


    Full Text Available Polymer-supported quaternary phosphonium salt (PS-QPS was explored as effective catalyst for the coupling reaction of carbon dioxide with epoxides. The results indicated that cyclic carbonates with high yields (98.6% and excellent selectivity (100% could be prepared at the conditions of 5 MPa CO2, 150°C, and 6 h without the addition of organic solvents or cocatalysts. The effects of various reaction conditions on the catalytic performance were investigated in detail. The catalyst is applicable to a variety of epoxides, producing the corresponding cyclic carbonates in good yields. Furthermore, the catalyst could be recovered easily and reused for five times without loss of catalytic activity obviously. A proposed mechanism for synthesis of cyclic carbonate in the presence of PS-QPS was discussed. The catalyst was characterized by thermogravimetric analysis (TGA, scanning electron microscopy (SEM, and Fourier transform infrared (FT-IR spectrum. It is believed that PS-QPS is of great potential for CO2 fixation applications due to its unusual advantages, such as easy preparation, high activity and selectivity, stability, low cost, and reusability.

  1. Theoretical study of the P-Ylide reaction in the carbon nanotube

    Institute of Scientific and Technical Information of China (English)

    XIAO Bo; ZHAO JingXiang; DING YiHong; SUN ChiaChung


    Recent studies have shown that the inner phase of carbon nanotubes (CNTs) can not only change the properties of molecules inside the tube,but also enhance or restrain the S_N2 reactions.Thus,the CNTs can be considered a form of solid solvent.In this paper,we study the[2+2]cycloaddition reaction between CH_2O and PH_3CH_2 in the gas phase,benzene solution and inner phase of CNT using the density functional theory (DFT).The results indicate that the inner phase of CNT has little effect on the[2+2]cycloaddition reaction.This can be explained as that while taking the linear arrangement for S_N2 reaction,the reactants do not possess the axial symmetry for the studied[2+2]cycloaddition reaction.Therefore,although the CNT has large axial polarizability,it can exert little influence on the[2+2]cycloaddition reaction.Our studies will be helpful for further understanding of the inner phase chemistry of CNTs.

  2. Theoretical study of the P-Ylide reaction in the carbon nanotube

    Institute of Scientific and Technical Information of China (English)


    Recent studies have shown that the inner phase of carbon nanotubes(CNTs) can not only change the properties of molecules inside the tube,but also enhance or restrain the SN2 reactions.Thus,the CNTs can be considered a form of solid solvent.In this paper,we study the [2+2] cycloaddition reaction between CH2O and PH3CH2 in the gas phase,benzene solution and inner phase of CNT using the density functional theory(DFT).The results indicate that the inner phase of CNT has little effect on the [2+2] cycloaddition reaction.This can be explained as that while taking the linear arrangement for SN2 reaction,the reactants do not possess the axial symmetry for the studied [2+2] cycloaddition reaction.Therefore,although the CNT has large axial polarizability,it can exert little influence on the [2+2] cycloaddition reaction.Our studies will be helpful for further understanding of the inner phase chemistry of CNTs.

  3. The neighboring effect of isosorbide and its epimers in their reactions with dimethyl carbonate

    Directory of Open Access Journals (Sweden)

    Fabio Aricò


    Full Text Available The reactions of isosorbide and its epimers, isomannide and isoidide, with dimethyl carbonate have been herein investigated as easy access to bio-based products by a free-halogen chemistry approach. Isosorbide and its epimers show a different reactivity in bimolecular nucleophilic substitution with dimethyl carbonate (DMC. Carboxymethylation reaction was carried out in the presence of DMC and a weak base resulting in the high-yielding synthesis of dicarboxymethyl derivatives. Isomannide was the most reactive anydro sugar due to the less sterically hindered exo position of the OH groups. On the other hand, methylation of isosorbide and its epimers, conducted in the presence of a strong base and DMC, showed the higher reactivity of the endo hydroxyl group, isoidide being the most reactive epimer. This result has been ascribed to the neighboring effect due to the combination of the oxygen in β-position and the intramolecular hydrogen bond within the anhydro sugar structure. Methylation reactions were also conducted in autoclave at high temperature with the amphoteric catalyst hydrotalcite using DMC as reagent and solvent. In this case, the reactivity of the epimers resulted quite differently with isosorbide being the most reactive reagent possibly as a result of the structure of hydrotalcite comprising of both acidic and basic sites. The neighboring effect was observed with good evidence in these methylation reactions.

  4. The calcium-alkali syndrome


    Arroyo, Mariangeli; Fenves, Andrew Z.; Emmett, Michael


    The milk-alkali syndrome was a common cause of hypercalcemia, metabolic alkalosis, and renal failure in the early 20th century. It was caused by the ingestion of large quantities of milk and absorbable alkali to treat peptic ulcer disease. The syndrome virtually vanished after introduction of histamine-2 blockers and proton pump inhibitors. More recently, a similar condition called the calcium-alkali syndrome has emerged as a common cause of hypercalcemia and alkalosis. It is usually caused b...

  5. Correlation between carbon-carbon bond length and the ease of retro Diels-Alder reaction

    Indian Academy of Sciences (India)

    Sambasivarao Kotha; Shaibal Banerjee; Mobin Shaikh


    The bond length between C8-C9 in (1′R,4′S,4a′R,8a′S)-6′,7′-dimethyl-1′,4′,4a′,8a′-tetrahydrospiro [cyclopropane-1,9′-[1,4]methanonaphthalene]-5′,8′-dione is 1.571 (2) Å and between C7-C12 is 1.567 (2) Å which are longer than the corresponding bond length for saturated bicyclic systems (1.531-1.535Å). This paper reports the correlation between bond length and the ease of retro Diels−Alder reaction.

  6. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    Directory of Open Access Journals (Sweden)

    Dengfeng Wang


    Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

  7. Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard


    A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

  8. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Krupka, Kenneth M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cantrell, Kirk J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  9. Polyaniline-Derived Ordered Mesoporous Carbon as an Efficient Electrocatalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Kai Wan


    Full Text Available Nitrogen-doped ordered mesoporous carbon was synthesized by using polyaniline as the carbon source and SBA-15 as the template. The microstructure, composition and electrochemical behavior were extensively investigated by the nitrogen sorption isotherm, X-ray photoelectron spectroscopy, cyclic voltammetry and rotating ring-disk electrode. It is found that the pyrolysis temperature yielded a considerable effect on the pore structure, elemental composition and chemical configuration. The pyrolysis temperature from 800 to 1100 °C yielded a volcano-shape relationship with both the specific surface area and the content of the nitrogen-activated carbon. Electrochemical tests showed that the electrocatalytic activity followed a similar volcano-shape relationship, and the carbon catalyst synthesized at 1000 °C yielded the best performance. The post-treatment in NH3 was found to further increase the specific surface area and to enhance the nitrogen doping, especially the edge-type nitrogen, which favored the oxygen reduction reaction in both acid and alkaline media. The above findings shed light on electrocatalysis and offer more strategies for the controllable synthesis of the doped carbon catalyst.

  10. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.


    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  11. Natural Alkali Shifts to the Methanol Business

    Institute of Scientific and Technical Information of China (English)


    @@ Inner Mongolia Yuanxing Natural Alkali Co., Ltd. (Natural Alkali SZ: 000683) established in 1997 is a large chemical enterprise with new energy as its leading business and natural gas chemicals and natural alkali chemicals as the supplement business.

  12. Thin film solid-state reactions forming carbides as contact materials for carbon-containing semiconductors (United States)

    Leroy, W. P.; Detavernier, C.; Van Meirhaeghe, R. L.; Lavoie, C.


    Metal carbides are good candidates to contact carbon-based semiconductors (SiC, diamond, and carbon nanotubes). Here, we report on an in situ study of carbide formation during the solid-state reaction between thin films. The solid-state reaction was examined between 11 transition metals (W, Mo, Fe, Cr, V, Nb, Mn, Ti, Ta, Zr, and Hf) and an amorphous carbon layer. Capping layers (C or TiN) of different thicknesses were applied to prevent oxidation. Carbide formation is evidenced for nine metals and the phases formed have been identified (for a temperature ranging from 100to1100°C). W first forms W2C and then WC; Mo forms Mo2C; Fe forms Fe3C; Cr first forms metastable phases Cr2C and Cr3C2-x, and finally forms Cr3C2; V forms VCx; Nb transforms into Nb2C followed by NbC; Ti forms TiC; Ta first forms Ta2C and then TaC; and Hf transforms into HfC. The activation energy for the formation of the various carbide phases has been obtained by in situ x-ray diffraction.

  13. Unique Sandwiched Carbon Sheets@Ni-Mn Nanoparticles for Enhanced Oxygen Evolution Reaction. (United States)

    Zhang, Yan; Zhang, Huijuan; Yang, Jiao; Bai, Yuanjuan; Qiu, Huajun; Wang, Yu


    A unique sandwich-like architecture, where Ni-Mn nanoparticles are enveloped in coupled carbon sheets (CS@Ni-Mn), has been successfully fabricated. In the synthesis process, a great quantity of uniform NiMnO3 nanosheets generated by a universal hydrothermal method acts as precursors and templates and the cheap, environmentally friendly and recyclable glucose functions as a green carbon source. Via subsequent hydrothermal reaction and thermal annealing, sandwiched nanocomposites with Ni-Mn nanoparticles embedded inside and carbon sheets encapsulating outside can be massively prepared. The novel sandwich-like CS@Ni-Mn possesses numerous advantages, such as an intrinsic porous feature, large specific surface area, and enhanced electronic conductivity. Moreover, as a promising NiMn-based oxygen evolution reaction (OER) catalyst, the special sandwiched nanostructure demonstrates improved electrochemical properties in 1 M KOH, including a low overpotential of about 250 mV, a modest Tafel slope of 40 mV dec(-1), excellent stability over 2000 cycles, and durability for 40 h.

  14. Coating of graphite flakes with MgO/carbon nanocomposite via gas state reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sharif, M., E-mail: [Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Faghihi-Sani, M.A. [Sharif University of Technology, Tehran (Iran, Islamic Republic of); Golestani-Fard, F. [Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Saberi, A. [Tabriz University (Iran, Islamic Republic of); Soltani, Ali Khalife [Iran University of Science and Technology, Tehran (Iran, Islamic Republic of)


    Coating of graphite flakes with MgO/carbon nanocomposite was carried out via gaseous state reaction between mixture of Mg metal, CO gas and graphite flakes at 1000 {sup o}C. XRD and FE-SEM analysis of coating showed that the coating was comprised of MgO nano particles and amorphous carbon distributed smoothly and covered the graphite surface evenly. Thermodynamic calculations were employed to predict the reaction sequences as well as phase stability. The effect of coating on water wettability and oxidation resistance of graphite was studied using contact angle measurement and TG analysis, respectively. It was demonstrated that the reaction between Mg and CO could result in MgO/C nanocomposite deposition. The coating improved water wettability of graphite and also enhanced the oxidation resistance of graphite flakes significantly. Also the graphite coating showed significant phenolic resin-wettabilty owing to high surface area of such hydrophilic nano composite coating. The importance of graphite coating is explained with emphasis on its potential application in graphite containing refractories.

  15. Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

    Institute of Scientific and Technical Information of China (English)

    张焕军; 朱国才


    The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor.The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined. The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determination of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process.The apparent activation energy was calculated to be 32.8kJ·mo1-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.

  16. Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng


    Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.

  17. Dilepton spectroscopy at intermediate energies; the carbon - carbon reaction at 1 GeV/A; Spectroscopie des dileptons aux energies intermediaires; la reaction carbone - carbone A 1 GeV/A

    Energy Technology Data Exchange (ETDEWEB)

    Prunet, M.


    The Physics context of this work is heavy ion collisions at relativistic energies where di-electron provide informations on the produced hot and dense nuclear matter. The experiment is performed by the DiLepton Spectrometer (DLS) Collaboration at the Lawrence Berkeley`s Bevalac. After a description of the apparatus, we review the whole program and the main results so far obtained: first evidence of a significant di-electron signal at energies above 1 GeV/A; improvement of the understanding of di-electron production (electromagnetic decays of hadrons, {pi}{sup +}{pi}{sup -} annihilation and hadronic Bremsstrahlung). The results of p-p, p-d reactions from 1 to 4.9 GeV/A show that hadronic Bremsstrahlung (pp, pn) should be reformulated. Our analysis, optimized on the reaction Carbon-Carbon at 1 GeV/A, has been applied to {alpha}-Ca and d-Ca. We have developed two main aspects: improvement of the time resolution (500 ps) in order to eliminate all of the protons. Improvement of the space resolution (300 {mu}) for better mass resolution, in particular in the {rho} region. We obtain the cross section of di-electron production as a function of mass, transverse momentum and rapidity from the C-C, {alpha}-Ca and d-Ca reactions at 1 GeV/A. We also compare the cross section for all of the measured systems at 1 GeV/A, including Ca-Ca, and we show a (ApAt){sup {alpha}} dependence with {alpha} {approx_equal} 1.1. A study of the associated multiplicity has also been performed. Nevertheless, the limited acceptance of the DLS and its poor mass resolution to identify the {rho}, {omega} vector mesons, do not allow to conclude on hadron behaviour in nuclear matter. This point is one of the main goal of the HADES project at GSI (Darmstadt), which we give a brief description of the main features. (authors). 60 refs.

  18. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nandan, Ravi, E-mail:; Nanda, Karuna Kar [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India)


    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  19. A high-performance metal-free hydrogen-evolution reaction electrocatalyst from bacterium derived carbon



    We report a sustainable approach to obtain carbon materials with nitrogen and phosphorus dual functionalities from a common bacterium strain (S. aureus) as a highly efficient hydrogen-evolution reaction (HER) catalyst. With mesoporous structure introduced by ZnCl2 salt and cathodic activation, it demonstrates an onset overpotential as low as 76 mV, a Tafel slope of 58.4 mV dec(-1) and a large normalized exchange current density of 1.72 x 10(-2) mA cm(-2), which are comparable to those of hith...

  20. Continuous reactions in supercritical carbon dioxide: problems, solutions and possible ways forward. (United States)

    Han, Xue; Poliakoff, Martyn


    This Tutorial Review focuses on supercritical carbon dioxide (scCO(2)), and discusses some of the problems that have frustrated its wide use on an industrial scale. It gives some recent examples where strategies have been developed to reduce the energy requirements, including sequential reactions and gas-expanded liquids. It then describes a number of cases where scCO(2) offers real chemical advantages over more conventional solvents, for example by controlled phase separation, tunable selectivity, oxidation and on-line analysis and self-optimisation. Overall, this review indicates where scCO(2) could deliver value in the future.

  1. Reinforced membrane based on crosslink reaction between water soluble sulfonated carbon nanotubes and sulfonated polystyrene (United States)

    Dai, Ying; Hong, Haiping; Welsh, Jeffry S.


    Reinforced films based on sulfonated polystyrene cross-linked with water-soluble sulfonated carbon nanotubes were fabricated using a free-standing film-making method. Transmission and scanning electron microscopy, X-ray photoelectron spectroscopy, and thermo-gravimetric analysis were used to verify the cross-linking reaction. The mechanical properties of these films demonstrated that the tensile strength increases with an increase in the sulfonated nanotube concentration. At 5 wt% nanotube loading, the tensile strength increased 84% compared with polymer containing no nanotube loading. The relationships between structure and mechanical properties are discussed and a possible direction for making ultra thin and ultra lightweight film is proposed

  2. Theoretical Study on the Reaction Mechanism between Dichlorocarbene and Armchair Single-walled Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    LI Rui-Fang; SHANG Zhen-Feng; XU Xiu-Fang; WANG Gui-Chang


    The reaction mechanism between CCl2 and armchair single-walled carbon nanotubes (ASWCNTs) (3,3) and (4,4) has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CCl2 adding to ASWCNT (3,3) and (4,4) are computed and compared. The lower barrier of CCl2 forms cycloaddition isomer on (3,3) maybe because the strain energy of (3,3) is larger than that of (4,4). Our theoretical results are consistent with the experimental results.

  3. Diameter Tuning of Single Walled Carbon Nanotubes with Reaction Temperature Using a Co Monometallic Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Li, N.; Wang, X; Ren, F; Haller, G; Pfefferle, L


    Metal incorporated MCM-41 has proven to be a valuable template for the growth of narrow distributions of single-walled carbon nanotubes (SWNT), producing samples with a wide range of different mean diameters. The ability to obtain narrow diameter distributions at different mean diameters is important for applications that require particular (n,m) nanotubes. Another advantage of this system is the ease of cleaning and low metal content as compared to bimetallic systems. In this Article, we show that Co-MCM-41 allows diameter tuning of SWNT produced over a broad diameter range (from 0.6-0.8 to 1.8-2.0 nm) by changing reaction temperature. The lower temperature reaction provides a robust means to obtain very small diameter SWNT. X-ray absorption experiments show that the change in SWNT diameter correlates with the change in metal particle size.

  4. Covalent grafting of carbon nanotubes with a biomimetic heme model compound to enhance oxygen reduction reactions. (United States)

    Wei, Ping-Jie; Yu, Guo-Qiang; Naruta, Yoshinori; Liu, Jin-Gang


    The oxygen reduction reaction (ORR) is one of the most important reactions in both life processes and energy conversion systems. The replacement of noble-metal Pt-based ORR electrocatalysts by nonprecious-metal catalysts is crucial for the large-scale commercialization of automotive fuel cells. Inspired by the mechanisms of dioxygen activation by metalloenzymes, herein we report a structurally well-defined, bio-inspired ORR catalyst that consists of a biomimetic model compound-an axial imidazole-coordinated porphyrin-covalently attached to multiwalled carbon nanotubes. Without pyrolysis, this bio-inspired electrocatalyst demonstrates superior ORR activity and stability compared to those of the state-of-the-art Pt/C catalyst in both acidic and alkaline solutions, thus making it a promising alternative as an ORR electrocatalyst for application in fuel-cell technology.

  5. Comparative temporal analysis of multiwalled carbon nanotube oxidation reactions: Evaluating chemical modifications on true nanotube surface (United States)

    Pacheco, Flávia G.; Cotta, Alexandre A. C.; Gorgulho, Honória F.; Santos, Adelina P.; Macedo, Waldemar A. A.; Furtado, Clascídia A.


    The influence of extensive purification on oxidized multiwalled carbon nanotube surface composition was studied through the characterization and differentiation of the actual surface submitted to three oxidation methods: microwave-assisted acid oxidation, hydrogen peroxide reflux, and Fenton reaction. The oxidized samples were purified by a multi-step procedure including the sequential use of basic reflux and dispersion in dimethylformamide (DMF). The results showed a significant increase in the amount of oxidation debris with hydrogen peroxide and Fenton reaction times longer than 8 h and strong surface characteristic modification. With regard to sample purification, basic reflux led to a reduction in oxygenated group concentration of only 10% in the samples treated by acid oxidation. On the other hand, the subsequent use of DMF led to a further decrease in concentration of 39%, proving to be a more efficient method for the removal of oxidation debris.

  6. Palladium on Carbon-Catalyzed Suzuki-Miyaura Coupling Reaction Using an Efficient and Continuous Flow System

    Directory of Open Access Journals (Sweden)

    Tomohiro Hattori


    Full Text Available The continuous flow Suzuki-Miyaura reaction between various haloarenes and arylboronic acids was successfully achieved within only ca. 20 s during the single-pass through a cartridge filled with palladium on carbon (Pd/C. No palladium leaching was observed in the collected reaction solution by atomic absorption spectrometry (detection limit: 1 ppm.

  7. Study of 16O(12C,α20Ne)α for the investigation of carbon-carbon fusion reaction via the Trojan Horse Method (United States)

    Rapisarda, G. G.; Spitaleri, C.; Bordeanu, C.; Hons, Z.; Kiss, G. G.; La Cognata, M.; Mrazek, J.; Nita, C.; Pantelica, D.; Petrascu, H.; Pizzone, R. G.; Romano, S.; Szücs, T.; Trache, L.; Tumino, A.; Velisa, G.


    Carbon-carbon fusion reaction represents a nuclear process of great interest in astrophysics, since the carbon burning is connected with the third phase of massive stars (M > 8 M⊙) evolution. In spite of several experimental works, carbon-carbon cross section has been measured at energy still above the Gamow window moreover data at low energy present big uncertainty. In this paper we report the results about the study of the 16O(12C,α 20Ne)α reaction as a possible three-body process to investigate 12C(12C,α)20Ne at astrophysical energy via Trojan Horse Method (THM). This study represents the first step of a program of experiments aimed to measure the 12C+12C cross section at astrophysical energy using the THM.

  8. Investigation of the reaction mechanism for the four-particle photodisintegration of a carbon nucleus (United States)

    Afanas'ev, S. N.; Gorbenko, E. S.; Khodyachikh, A. F.


    The four-particle photodisintegration of a carbon nucleus in the reactions 12C(γ, p)3H2α and 12C(γ, n)3H2α is investigated by a method that employs a diffusion chamber in a magnetic field. It is shown that these reactions proceed according a sequential-type scheme: excited states of 11B and 11C nuclei decay to weakly excited states of 8Be, 7Li, and 7Be nuclei. It is concluded that nucleons are knocked out from the s shell. In the excitation curve for the 2α system in the reaction 12C(γ, p)3H2α, a resonance is found between the maxima corresponding to the ground and the first excited state of the 8Be nucleus, and this resonance is identified as a ghost anomaly. The branching fractions of the decay modes are determined. The angular distributions of nucleons in the reaction c.m. frame are measured. The energy dependence of the asymmetry coefficient for the angular distributions is obtained. A fast increase in this coefficient is observed in the energy range 38 40 MeV. It is concluded that the asymmetry coefficient depends on the excitation energy of the final nucleus in the region of intermediate photon energies.

  9. A laboratory study of the heterogeneous reaction of nitric acid on calcium carbonate particles (United States)

    Goodman, A. L.; Underwood, G. M.; Grassian, V. H.


    It has been postulated that the reaction of nitric acid with calcium carbonate, namely, CaCO3(s) + 2HNO3(g) → Ca(NO3)2(s) + CO2(g) + H2O(g), plays an important role in the atmosphere. In this study, transmission FTIR spectroscopy, diffuse reflectance UV-visible spectroscopy, transmission electron microscopy and a Knudsen cell reactor coupled to a quadrupole mass spectrometer have been used to investigate the heterogeneous reactivity of HNO3 on CaCO3 at 295 K as a function of relative humidity. Transmission FTIR spectroscopy was used to probe both gas-phase and adsorbed products and showed that the reaction of HNO3 and CaCO3 is limited to the surface of the CaCO3 particle in the absence of adsorbed water. However, in the presence of water vapor, the reaction is greatly enhanced and is not limited to the surface of the particle producing both solid calcium nitrate and gaseous carbon dioxide. The enhanced reactivity of the particles is attributed to the presence of a layer of adsorbed water on the particle surface. The amount of adsorbed water on the particle surface is strongly dependent on the extent of the reaction. This can be understood in terms of the increased hydrophilicity of calcium nitrate as compared to calcium carbonate. Data from experiments using a mass-calibrated Knudsen cell reactor showed the stoichiometry for the reaction determined from gas-phase species deviated from that expected from the balanced equation. Water adsorption on the particle surface and gases dissolved into the water layer appear to be the cause of this discrepancy. The measured uptake coefficient accounting for the BET area of the sample is determined to be 2.5±0.1×10-4 for HNO3 on CaCO3 under dry conditions and is found to increase in the presence of water vapor. Atmospheric implications of the results presented here are discussed.

  10. Alkali metal and alkali earth metal gadolinium halide scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.


    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  11. The reaction of carbon disulphide with -haloketones and primary amines in the presence of potassium iodide as catalyst

    Indian Academy of Sciences (India)

    Javad Safaei-Ghomi; Fariba Salimi; Ali Ramazani


    A simple, mild and convenient method has been developed for the synthesis of 3,4,5-trialkyl-1,3-thiazole-2(3)-thione derivatives through one pot three-component reaction between a primary amine, carbon disulphide, and -haloketone in the presence of potassium iodide at room temperature conditions. The products were obtained with excellent yield and appropriate reaction times. This reaction represents a rapid and unprecedented route to the described molecules that have biological specifications.

  12. Phase Evolution in Boride-Based Cermets and Reaction Bonding onto Plain Low Carbon Steel Substrate (United States)

    Palanisamy, B.; Upadhyaya, A.


    Reaction sinter bonding is a process that aims to bond two materials for improvement in properties through reactive sintering technique. The process has been effectively used to sinter hard materials like borides in situ which not only possess excellent oxidation resistance, good corrosion resistance but also resistant to abrasive wear. Sinter bonding is a unique surface modification process achieved through powder metallurgy and is competent with other techniques like boronizing sintering and sinter-brazing since it eliminates the additional operations of heat treatment and assembly and removes the inherent setbacks with these processes. This study focuses on identifying the phase evolution mechanism using characterization tools like x-ray diffractometry and energy dispersive spectroscopy and study of sinter bonding of the boron containing precursors (Mo-Cr-Fe-Ni-FeB-MoB) onto plain carbon steel. A microstructure containing Fe-based matrix dispersed with complex borides develops with temperature in the tape cast sheets. A fivefold increase in hardness between plain carbon steel in wrought condition and sinter bonded steel was observed. The multilayer consisted of a reaction zone adjacent to the interface and was investigated with the composition profile and hardness measurements. A model of sinter bonding between the cermet and the steel has also been proposed.

  13. Effect of denitrifying bacteria on the electrochemical reaction of activated carbon fiber in electrochemical biofilm system

    Institute of Scientific and Technical Information of China (English)

    YING Diwen; JIA Jinping; ZHANG Lehua


    An electrochemical-activated denitrifying biofilm system consisting of activated carbon fiber electrodes immobilized with denitrifying bacteria film as cathode was studied.A revised model for an electrochemical-activated denitrifying biofilm was developed and validated by electrochemical analysis of cathodal polarization curves and nitrate consumption rate.The cathodal polarization curve and nitrate consumption rate were introduced to verify the rate of electrochemical reaction and the activity of denitrifying bacteria,respectively.It was shown that the denitrification process effectively strengthened the electrochemical reaction while the electron also intensified denitrification activity.Electron was transferred between electrochemical process and biological process not only by hydrogen molecule but also by new produced active hydrogen atom.Additionally,a parameter of apparent exchange current density was deprived from the cathodal polarization curve with high overpotential,and a new bio-effect current density was defined through statistical analysis,which was linearly dependent to the activity of denitrification bacteria.Activated carbon fiber (ACF) electrode was also found to be more suitable to the electrochemical denitrifying system compared with graphite and platinum.

  14. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts (United States)

    Senanayake, Sanjaya D.; Pappoe, Naa Adokaley; Nguyen-Phan, Thuy-Duong; Luo, Si; Li, Yuanyuan; Xu, Wenqian; Liu, Zongyuan; Mudiyanselage, Kumudu; Johnston-Peck, Aaron C.; Frenkel, Anatoly I.; Heckler, Ilana; Stacchiola, Dario; Rodriguez, José A.


    We have studied the catalytic carbon monoxide (CO) oxidation (CO + 0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5 wt.% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including transmission electron microscopy (TEM), the local catalyst morphology and structure were also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggest that surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.

  15. Cu,N-codoped Hierarchical Porous Carbons as Electrocatalysts for Oxygen Reduction Reaction. (United States)

    Yu, Haiyan; Fisher, Adrian; Cheng, Daojian; Cao, Dapeng


    It remains a huge challenge to develop nonprecious electrocatalysts with high activity to substitute commercial Pt catalysts for oxygen reduction reactions (ORR). Here, the Cu,N-codoped hierarchical porous carbon (Cu-N-C) with a high content of pyridinic N was synthesized by carbonizing Cu-containing ZIF-8. Results indicate that Cu-N-C shows excellent ORR electrocatalyst properties. First of all, it nearly follows the four-electron route, and its electron transfer number reaches 3.92 at -0.4 V. Second, both the onset potential and limited current density of Cu-N-C are almost equal to those of a commercial Pt/C catalyst. Third, it exhibits a better half-wave potential (∼16 mV) than a commercial Pt/C catalyst. More importantly, the Cu-N-C displays better stability and methanol tolerance than the Pt/C catalyst. All of these good properties are attributed to hierarchical structure, high pyridinic N content, and the synergism of Cu and N dopants. The metal-N codoping strategy can significantly enhance the activity of electrocatalysts, and it will provide reference for the design of novel N-doped porous carbon ORR catalysts.

  16. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells (United States)

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


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

  17. The key role of metal dopants in nitrogen-doped carbon xerogel for oxygen reduction reaction (United States)

    Liu, Sisi; Deng, Chengwei; Yao, Lan; Zhong, Hexiang; Zhang, Huamin


    Highly active non-precious metal catalysts based on nitrogen-doped carbon xerogel (NCX) for the oxygen reduction reaction (ORR) is prepared with resorcinol(R)-formaldehyde (F) resin as carbon precursor and NH3 as nitrogen source. NCX samples doped with various transition metal species are investigated to elucidate the effect of transition metals on the structure and ORR activity of the products. As-prepared NCX catalysts with different metals are characterized using nitrogen-adsorption analysis, X-ray diffractometry, X-ray photoelectron spectroscopy, and Raman spectroscopy. The structural properties and ORR activities of the catalysts are altered by addition of different metals, and NCX doped with iron exhibits the best ORR activity. Metal doping evidently promotes the formation of more micropores and mesopores. Raman and XPS studies reveal that iron, cobalt, and nickel can increase pyridinic-N contents and that iron can catalyse the formation of graphene structures and enhance quaternary-N contents. Whereas the total N-content does not determine ORR activity, Metal-N4/C-like species generated from the interaction of the metals with nitrogen and carbon atoms play important roles in achieving high ORR activity.

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

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


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

  19. Evaluation and characterization of the methane-carbon dioxide decomposition reaction (United States)

    Davenport, R. J.; Schubert, F. H.; Shumar, J. W.; Steenson, T. S.


    A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

  20. Revealing Brown Carbon Chromophores Produced in Reactions of Methylglyoxal with Ammonium Sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Peng; Laskin, Julia; Nizkorodov, Sergey A.; Laskin, Alexander


    Atmospheric brown carbon (BrC) is an important contributor to light absorption and climate forcing by aerosols. Reactions between small water-soluble carbonyls and ammonia or amines have been identified as one of the potential pathways of BrC formation. However, detailed chemical characterization of BrC chromophores has been challenging and their formation mechanisms are still poorly understood. Understanding BrC formation is impeded by the lack of suitable methods which can unravel the variability and complexity of BrC mixtures. This study applies high performance liquid chromatography (HPLC) coupled to photodiode array (PDA) detector and high resolution mass spectrometry (HRMS) to investigate optical properties and chemical composition of individual BrC components produced through reactions of methylglyoxal (MG) and ammonium sulfate (AS), both of which are abundant in the atmospheric environment. A direct relationship between optical properties and chemical composition of 30 major BrC chromophores was established. Nearly all of these chromophores are nitrogen-containing compounds that account for >70% of the overall light absorption by the MG+AS system in the 300-500 nm range. These results suggest that reduced-nitrogen organic compounds formed in reactions between atmospheric carbonyls and ammonia/amines are important BrC chromophores. It is also demonstrated that improved separation of BrC chromophores by HPLC will significantly advance understanding of BrC chemistry.

  1. Localized surface grafting reactions on carbon nanofibers induced by gamma and e-beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Evora, M.C., E-mail: [Institute for Advanced Studies-IEAV/DCTA, Av. Cel Jose Alberto Albano do Amarante, 1-Putim, 12228-001 São Jose dos Campos, SP (Brazil); Araujo, J.R., E-mail: [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Ferreira, E.H.M. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Strohmeier, B.R. [Thermo Fisher Scientific, 5225 Verona Road, Madison, WI 53711 (United States); Silva, L.G.A., E-mail: [Institute for Nuclear and Energy Research- IPEN, Av. Prof lineu Prestes, 2242- Cidade Universitaria, 05508-000 SP (Brazil); Achete, C.A. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil)


    Graphical abstract: - Highlights: • Methodology for the functionalization of carbon nanofibers was investigated. • Two radiation sources were used to promote grafting reactions: gamma and electron beam. • We report the optimum inhibitor concentration to achieve the functionalization. • Surface of carbon nanofibers showed an increase of oxygen content after irradiation. • The radiation-induced graphitization did not damage the overall sp{sup 2} structure. - Abstract: Electron beam and gamma-ray irradiation have potential application to modify the carbon fiber nanostructures in order to produce useful defects in the graphitic structure and create reactive sites. In this study, the methodology to functionalize carbon nanofiber (CNF), via a radiation process and using acrylic acid as a source of oxygen functional groups, was investigated. The samples were submitted to a direct grafting radiation process with electron beam and gamma-ray source. Several parameters were changed such as: acrylic acid concentration, radiation dose and percentage of inhibitor necessary to achieve functionalization, with higher percentage of oxygen functional groups on CNF surface, and better dispersion. The better results achieved were when mixing CNF in a solution of acrylic acid with 6% of inhibitor (FeSO{sub 4}·7H{sub 2}O) and irradiated at 100 kGy. The samples were characterized by X-ray photoelectron spectroscopy and the surface composition (atomic%) showed a significant increase of oxygen content for the samples after irradiation. Also, the dispersion of the functionalized CNF in water was stable during months which may be a good indication that the functionalization process of CNF via ionizing radiation was successful.

  2. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama


    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  3. Differentiation of chemical reaction activity of various carbon nanotubes using redox potential: Classification by physical and chemical structures. (United States)

    Tsuruoka, Shuji; Matsumoto, Hidetoshi; Castranova, Vincent; Porter, Dale W; Yanagisawa, Takashi; Saito, Naoto; Kobayashi, Shinsuke; Endo, Morinobu


    The present study systematically examined the kinetics of a hydroxyl radical scavenging reaction of various carbon nanotubes (CNTs) including double-walled and multi-walled carbon nanotubes (DWCNTs and MWCNTs), and carbon nano peapods (AuCl3@DWCNT). The theoretical model that we recently proposed based on the redox potential of CNTs was used to analyze the experimental results. The reaction kinetics for DWCNTs and thin MWCNTs agreed well with the theoretical model and was consistent with each other. On the other hand, thin and thick MWCNTs behaved differently, which was consistent with the theory. Additionally, surface morphology of CNTs substantially influenced the reaction kinetics, while the doped particles in the center hollow parts of CNTs (AuCl3@DWCNT) shifted the redox potential in a different direction. These findings make it possible to predict the chemical and biological reactivity of CNTs based on the structural and chemical nature and their influence on the redox potential.

  4. Pathways of birnessite formation in alkali medium

    Institute of Scientific and Technical Information of China (English)

    FENG Xionghan; TAN Wenfeng; LIU Fan; HUANG Qiaoyun; LIU Xiangwen


    Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), energy dispersed X-ray analysis (EDAX), infrared spectroscopy (IR) techniques and chemical composition analysis, Eh-pH equilibrium diagram approaches were employed to investigate the reaction process and pathways of birnessite formation. Results showed that the process of the birnessite formation could be divided into four stages: (1) formation stage for hausmannite and feitknechtite, (2) stage of transformation of hausmannite and feitknechtite to buserite, (3) buserite crystal growing stage, and (4) stage of conversion of buserite into birnessite. Mn(OH)2 was mainly present as amorphous state only for a short initial time of oxidation reaction. In the oxidation process, buserite formed following two pathways by recrystallization after dissolution of the intermediates, and the transformations of the minerals depended on the Eh determined by the dissolved O2 concentration on their surfaces. The results are fundamental in further exploration on the mechanism of birnessite formation in the alkali medium. A great practical significance would also be expected with respect to the areas of material sciences.

  5. Utilization of Mineral Wools as Alkali-Activated Material Precursor

    Directory of Open Access Journals (Sweden)

    Juho Yliniemi


    Full Text Available Mineral wools are the most common insulation materials in buildings worldwide. However, mineral wool waste is often considered unrecyclable because of its fibrous nature and low density. In this paper, rock wool (RW and glass wool (GW were studied as alkali-activated material precursors without any additional co-binders. Both mineral wools were pulverized by a vibratory disc mill in order to remove the fibrous nature of the material. The pulverized mineral wools were then alkali-activated with a sodium aluminate solution. Compressive strengths of up to 30.0 MPa and 48.7 MPa were measured for RW and GW, respectively, with high flexural strengths measured for both (20.1 MPa for RW and 13.2 MPa for GW. The resulting alkali-activated matrix was a composite-type in which partly-dissolved fibers were dispersed. In addition to the amorphous material, sodium aluminate silicate hydroxide hydrate and magnesium aluminum hydroxide carbonate phases were identified in the alkali-activated RW samples. The only crystalline phase in the GW samples was sodium aluminum silicate. The results of this study show that mineral wool is a very promising raw material for alkali activation.

  6. Cobalt diselenide nanoparticles embedded within porous carbon polyhedra as advanced electrocatalyst for oxygen reduction reaction (United States)

    Wu, Renbing; Xue, Yanhong; Liu, Bo; Zhou, Kun; Wei, Jun; Chan, Siew Hwa


    Highly efficient and cost-effective electrocatalyst for the oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications. Herein, strongly coupled hybrid composites composed of cobalt diselenide (CoSe2) nanoparticles embedded within graphitic carbon polyhedra (GCP) as high-performance ORR catalyst have been rationally designed and synthesized. The catalyst is fabricated by a convenient method, which involves the simultaneous pyrolysis and selenization of preformed Co-based zeolitic imidazolate framework (ZIF-67). Benefiting from the unique structural features, the resulting CoSe2/GCP hybrid catalyst shows high stability and excellent electrocatalytic activity towards ORR (the onset and half-wave potentials are 0.935 and 0.806 V vs. RHE, respectively), which is superior to the state-of-the-art commercial Pt/C catalyst (0.912 and 0.781 V vs. RHE, respectively).

  7. A sensitive biosensor for the fluorescence detection of the acetylcholinesterase reaction system based on carbon dots. (United States)

    Ren, Xiangling; Wei, Jianfei; Ren, Jun; Qiang, Li; Tang, Fangqiong; Meng, Xianwei


    The carbon dots (C-dots) with high fluorescence quantum yield were prepared using hydrothermal method. C-dots have been adopted as probes for the fluorescence turn-off detection of H2O2 based on the special sensibility for the hydroxyl radical. And then the biosensors for the detection of substrate and enzymes activities were established in the acetylcholinesterase reaction system, which were related to the production of H2O2. Specifically, the proposed fluorescent biosensor was successfully applied to detect the concentration of choline (in the range from 0.025 to 50 μM) and acetylcholine (in the range from 0.050 to 50 μM), and the activity of choline oxidase (in the range from 1 to 75 U/L) and acetylcholinesterase (1 to 80 U/L). These results showed a sensitive, universal, nontoxic and eco-friendly detecting technique has been developed.

  8. Assesment of Alkali Resistance of Basalt Used as Concrete Aggregates

    Directory of Open Access Journals (Sweden)

    al-Swaidani Aref M.


    Full Text Available The objective of this paper is to report a part of an ongoing research on the influence of using crushed basalt as aggregates on one of durability-related properties of concrete (i.e. alkali-silica reaction which is the most common form of Alkali-Aggregate Reaction. Alkali resistance has been assessed through several methods specified in the American Standards. Results of petrographic examination, chemical test (ASTM C289 and accelerated mortar bar test (ASTM C1260 have particularly been reported. In addition, the weight change and compressive strength of 28 days cured concrete containing basaltic aggregates were also reported after 90 days of exposure to 10% NaOH solution. Dolomite aggregate were used in the latter test for comparison. The experimental results revealed that basaltic rocks quarried from As-Swaida’a region were suitable for production of aggregates for concrete. According to the test results, the studied basalt aggregates can be classified as innocuous with regard to alkali-silica reaction. Further, the 10% sodium hydroxide attack did not affect the compressive strength of concrete.

  9. Metal-Organic Framework Derived Hierarchically Porous Nitrogen-Doped Carbon Nanostructures as Novel Electrocatalyst for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang; Zhu, Chengzhou; Zhou, Yazhou; Yang, Guohai; Jeon, Ju Won; Lemmon, John P.; Du, Dan; Nune, Satish K.; Lin, Yuehe


    The hierarchically porous nitrogen-doped carbon materials, derived from nitrogen-containing isoreticular metal-organic framework-3 (IRMOF-3) through direct carbonization, exhibited excellent electrocatalytic activity in alkaline solution for oxygen reduction reaction (ORR). This high activity is attributed to the 10 presence of high percentage of quaternary and pyridinic nitrogen, the high surface area as well as good conductivity. When IRMOF-3 was carbonized at 950 °C (CIRMOF-3-950), it showed four-electron reduction pathway for ORR and exhibited better stability (about 78.5% current density was maintained) than platinum/carbon (Pt/C) in the current durability test. In addition, CIRMOF-3-950 presented high selectivity to cathode reactions compared to commercial Pt/C.

  10. Method for increasing -SiC yield on solid state reaction of coal fly ash and activated carbon powder

    Indian Academy of Sciences (India)

    Sulardjaka; Jamasri; M W Wildan; Kusnanto


    A novel process for increasing -SiC yield on solid state reaction of coal fly ash and micro powder activated carbon powder has been proposed. -SiC powder was synthesized at temperature 1300°C for 2 h under vacuum condition with 1 l/min argon flow. Cycling synthesis process has been developed for increasing -SiC yield on solid state reaction of coal fly ash and activated carbon powder. Synthesized products were analyzed by XRD with Cu-K radiation, FTIR spectrometer and SEM fitted with EDAX. The results show that the amount of relative -SiC is increased with the number of cycling synthesis.

  11. Bio-mass derived mesoporous carbon as superior electrode in all vanadium redox flow battery with multicouple reactions (United States)

    Ulaganathan, Mani; Jain, Akshay; Aravindan, Vanchiappan; Jayaraman, Sundaramurthy; Ling, Wong Chui; Lim, Tuti Mariana; Srinivasan, Madapusi P.; Yan, Qingyu; Madhavi, Srinivasan


    We first report the multi-couple reaction in all vanadium redox flow batteries (VRFB) while using bio-mass (coconut shell) derived mesoporous carbon as electrode. The presence of V3+/V4+ redox couple certainly supplies the additional electrons for the electrochemical reaction and subsequently provides improved electrochemical performance of VRFB system. The efficient electro-catalytic activity of such coconut shell derived high surface area mesoporous carbon is believed for the improved cell performance. Extensive power and electrochemical studies are performed for VRFB application point of view and described in detail.

  12. Effect of Co in the efficiency of the methanol electrooxidation reaction on carbon supported Pt

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Fernandez, P.; Montiel, M.; Ocon, P. [Dpto. Quimica-Fisica Aplicada, Facultad de Ciencias, Universidad Autonoma de Madrid (UAM), C/Francisco Tomas y Valiente 7, 28049 Madrid (Spain); Fierro, J.L.G.; Rojas, S. [Grupo de Energia y Quimica Sostenibles, Instituto de Catalisis y Petroleoquimica (CSIC), C/ Marie Curie 2, 28049 Madrid (Spain); Wang, H.; Abruna, H.D. [Department of Chemistry and Chemical Biology, Cornell University. Ithaca, NY 14853 (United States)


    The effect of Co addition to carbon nanotubes supported Pt in the methanol oxidation reaction has been investigated by means of differential electrochemical mass spectrometry (DEMS). It has been observed that the CO{sub 2} efficiency increases in carbon nanotubes supported PtCo compared to its homologous Pt catalysts, especially at potentials lower than 0.55 V. Despite of this, the Faradaic current reached by the bimetallic catalysts in the methanol electrooxidation was lower than those recorded on the monometallic samples. This is because Co addition difficult finding enough Pt vicinal sites for methanol dehydrogenation. On the other hand, it has been found that alloying Pt with Co, shifts down the d-band center of the larger element, so the strength of the interaction with adsorbates decreases. Consequently, it will be easier to oxidize CO{sub ad} on the bimetallic surface. Furthermore, the necessary -OH{sub ad} species for the CO{sub ad} oxidation to CO{sub 2} will be provided by the CNTs themselves. (author)

  13. Carbon fragmentation measurements and validation of the Geant4 nuclear reaction models for hadrontherapy (United States)

    De Napoli, M.; Agodi, C.; Battistoni, G.; Blancato, A. A.; Cirrone, G. A. P.; Cuttone, G.; Giacoppo, F.; Morone, M. C.; Nicolosi, D.; Pandola, L.; Patera, V.; Raciti, G.; Rapisarda, E.; Romano, F.; Sardina, D.; Sarti, A.; Sciubba, A.; Scuderi, V.; Sfienti, C.; Tropea, S.


    Nuclear fragmentation measurements are necessary when using heavy-ion beams in hadrontherapy to predict the effects of the ion nuclear interactions within the human body. Moreover, they are also fundamental to validate and improve the Monte Carlo codes for their use in planning tumor treatments. Nowadays, a very limited set of carbon fragmentation cross sections are being measured, and in particular, to our knowledge, no double-differential fragmentation cross sections at intermediate energies are available in the literature. In this work, we have measured the double-differential cross sections and the angular distributions of the secondary fragments produced in the 12C fragmentation at 62 A MeV on a thin carbon target. The experimental data have been used to benchmark the prediction capability of the Geant4 Monte Carlo code at intermediate energies, where it was never tested before. In particular, we have compared the experimental data with the predictions of two Geant4 nuclear reaction models: the Binary Light Ions Cascade and the Quantum Molecular Dynamic. From the comparison, it has been observed that the Binary Light Ions Cascade approximates the angular distributions of the fragment production cross sections better than the Quantum Molecular Dynamic model. However, the discrepancies observed between the experimental data and the Monte Carlo simulations lead to the conclusion that the prediction capability of both models needs to be improved at intermediate energies.

  14. Electrocatalytic activity of nitrogen doped carbon nanotubes with different morphologies for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Chen Zhu; Higgins, Drew [Department of Chemical Engineering, Waterloo Institute for Nanotechnology, Waterloo Institute for Sustainable Energy, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada); Chen Zhongwei, E-mail: zhwchen@uwaterloo.c [Department of Chemical Engineering, Waterloo Institute for Nanotechnology, Waterloo Institute for Sustainable Energy, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada)


    Nitrogen doped carbon nanotubes (NCNTs) were synthesized by a single step chemical vapor deposition technique using either ferrocene or iron(II) phthalocyanine as catalyst and pyridine as the carbon and nitrogen precursor. Variations in surface morphology and electrocatalytic activity for oxygen reduction reaction (ORR) were observed between the NCNTs synthesized using different catalysts. The structural and chemical characterizations were carried out using transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The electrochemical activity of NCNTs was evaluated with rotating ring disc electrode (RRDE) voltammetry. Structural characterization suggested more defects formed on the NCNTs synthesized from ferrocene (Fc-NCNTs) which led to a rugged surface morphology compared to the NCNTs synthesized from iron(II) phthalocyanine (FePc-NCNTs). Based on the RRDE voltammetry study, Fc-NCNTs demonstrated much higher activity for ORR than FePc-NCNT. Evidences from the structural and chemical characterizations illustrate the potential impact of catalyst structure in shaping the surface structure of NCNTs and the positive effect of surface defects on ORR activity. These results showed that potential improvements on ORR activity of NCNTs could be achieved by tailoring the surface structure of NCNTs by using catalysts with different structures.

  15. DNA-directed growth of Pd nanocrystals on carbon nanotubes towards efficient oxygen reduction reactions. (United States)

    Zhang, Lian Ying; Guo, Chun Xian; Cui, Zhiming; Guo, Jun; Dong, Zhili; Li, Chang Ming


    Unique DNA-promoted Pd nanocrystals on carbon nanotubes (Pd/DNA-CNTs) are synthesized for the first time, in which through its regularly arranged PO(4)(3-) groups on the sugar-phosphate backbone, DNA directs the growth of ultrasmall Pd nanocrytals with an average size of 3.4 nm uniformly distributed on CNTs. The Pd/DNA-CNT catalyst shows much more efficient electrocatalytic activity towards oxygen reduction reaction (ORR) with a much more positive onset potential, higher catalytic current density and better stability than other Pd-based catalysts including Pd nanocrystals on carbon nanotubes (Pd/CNTs) without the use of DNA and commercial Pd/C catalyst. In addition, the Pd/DNA-CNTs catalyst provides high methanol tolerance. The high electrocatalytic performance is mainly contributed by the ultrasmall Pd nanocrystal particles grown directed by DNA to enhance the mass transport rate and to improve the utilization of the Pd catalyst. This work may demonstrate a universal approach to fabricate other superior metal nanocrystal catalysts with DNA promotion for broad applications in energy systems and sensing devices.

  16. Mistletoe alkali inhibits peroxidation in rat liver and kidney

    Institute of Scientific and Technical Information of China (English)

    Zheng-Ming Shi; Ping Feng; Dong-Qiao Jiang; Xue-Jiang Wang


    AIM: To explore the antioxidant and free radical scavenger properties of mistletoe alkali (MA).METHODS: The antioxidant effect of mistletoe alkali on the oxidative stress induced by carbon tetrachloride (CCl4) in rats was investigated. The rats were divided into four groups (n = 8): CCl4-treated group (1 mL/kg body weight), MA -treated group (90 mg/kg), CCl4+MA-treated group and normal control group. After 4 wk of treatment,the level of malondialdehyde (MDA), a lipid peroxidation product (LPO) was measured in serum and homogenates of liver and kidney. Also, the level of glutathione (GSH),and activities of glutathione reductase (GR), glutathione peroxidase (GSPx), superoxide dismutase (SOD), and glutathione-S-transferase (GST) in liver and kidney were determined. Scavenging effects on hydroxyl free radicals produced in vitro by Fenton reaction were studied by ESR methods using 5,5-dimethyl-1-pyrroline-N-oxidesource. Urinary 8-hydroxydeoxyguanosine (8-OHdG) was determined by competitive ELISA.RESULTS: In CCl4-treated group, the level of LPO in serum of liver and kidney was significantly increased compared to controls. The levels of GSH and enzyme activities of SOD, GSPx and GR in liver and kidney were significantly decreased in comparison with controls. In CCl4+MA-treated group, the changes in the levels of LPO in serum of liver and kidney were not statistically significant compared to controls. The levels of SOD, GSPx and GR in liver and kidney were significantly increased in comparison with controls. There was a significant difference in urinary excretion of 8-OHdG between the CCl4-treated and MA-treated groups.CONCLUSION: Oxidative stress may be a major mechanism for the toxicity of CCl4. MA has a protective www.wjgnet.comeffect against CCl4 toxicity by inhibiting the oxidative damage and stimulating GST activities. Thus, clinical application of MA should be considered in cases with carbon tetrachloride-induced injury.

  17. Quantum Chemical Study on a New Mechanism of One-carbon Unit Transfer Reaction:The Water-assisted Mechanism

    Institute of Scientific and Technical Information of China (English)

    QIAO,Qing-An(乔青安); CAI,Zheng-Ting(蔡政亭); FENG,Da-Cheng(冯大诚)


    It is a theoretical study on the water-assisted mechanism of one-carbon unit transfer reaction, in which the energy barrier for each transition state lowered by about 80-100 kJ/mol when compared with the one in no-water-involved mechanism. The water-assisted path 4 is the favorite reaction way. Our results well explained the presumption from experiments.

  18. Reproducibly creating hierarchical 3D carbon to study the effect of Si surface functionalization on the oxygen reduction reaction (United States)

    Zeng, Yuze; Flores, Jose F.; Shao, Yu-Cheng; Guo, Jinghua; Chuang, Yi-De; Lu, Jennifer Q.


    We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This investigation reveals for the first time that non-conductive Si with an appropriate electronic structure distorts the carbon electronic structure and consequently enhances ORR electrocatalysis. The strong interface provides excellent electron connectivity according to electrochemical analysis. This highly reproducible and stable 3D platform can serve as a stepping-stone for the investigation of the effect of carbon surface functionalization on electrochemical reactions in general.We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This

  19. Food composition and acid-base balance: alimentary alkali depletion and acid load in herbivores. (United States)

    Kiwull-Schöne, Heidrun; Kiwull, Peter; Manz, Friedrich; Kalhoff, Hermann


    Alkali-enriched diets are recommended for humans to diminish the net acid load of their usual diet. In contrast, herbivores have to deal with a high dietary alkali impact on acid-base balance. Here we explore the role of nutritional alkali in experimentally induced chronic metabolic acidosis. Data were collected from healthy male adult rabbits kept in metabolism cages to obtain 24-h urine and arterial blood samples. Randomized groups consumed rabbit diets ad libitum, providing sufficient energy but variable alkali load. One subgroup (n = 10) received high-alkali food and approximately 15 mEq/kg ammonium chloride (NH4Cl) with its drinking water for 5 d. Another group (n = 14) was fed low-alkali food for 5 d and given approximately 4 mEq/kg NH4Cl daily for the last 2 d. The wide range of alimentary acid-base load was significantly reflected by renal base excretion, but normal acid-base conditions were maintained in the arterial blood. In rabbits fed a high-alkali diet, the excreted alkaline urine (pH(u) > 8.0) typically contained a large amount of precipitated carbonate, whereas in rabbits fed a low-alkali diet, both pH(u) and precipitate decreased considerably. During high-alkali feeding, application of NH4Cl likewise decreased pH(u), but arterial pH was still maintained with no indication of metabolic acidosis. During low-alkali feeding, a comparably small amount of added NH4Cl further lowered pH(u) and was accompanied by a significant systemic metabolic acidosis. We conclude that exhausted renal base-saving function by dietary alkali depletion is a prerequisite for growing susceptibility to NH4Cl-induced chronic metabolic acidosis in the herbivore rabbit.

  20. Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis. (United States)

    Geng, Jing; Wang, Wen-Liang; Yu, Yu-Xiang; Chang, Jian-Min; Cai, Li-Ping; Shi, Sheldon Q


    The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin.

  1. The kinetics of the O2/CO2 reaction in molten carbonate - Reaction orders for O2 and CO2 on NiO. [in fuel cells (United States)

    Winnick, J.; Ross, P. N.


    The kinetics of the O2/CO2 reaction in molten carbonate is investigated using paste electrolytes and nickel sinter electrodes. A two-step approach to the determination of reaction orders is employed. First, exchange currents at various P(CO2) and P(O2) were measured using the low polarization method. Second, alpha(+) and alpha(-) values were obtained from the slope of the Allen-Hickling plot for current densities low enough so that concentration polarization within the electrode can be neglected. The reaction orders are + 1/4 in CO2 and + 5/8 in O2 in the cathodic direction, and - 3/4 in CO2 and + 1/8 in O2 in the anodic direction.

  2. Study on the Influence of Carbonization Tower Operation on the Total Alkali Content of the Production Process of Baking Soda%小苏打生产工艺之碳化塔运行对总碱量的影响初探

    Institute of Scientific and Technical Information of China (English)



    将着重分析对碳化塔的运行控制和碳化工序原理及流程,通过分析碳化工序对小苏打质量、总碱量的稳定和存在问题,并采取针对性的措施,以降低消耗,稳定产品质量,以期提高小苏打产品在市场中的竞争力。%This paper focuses on the analysis of the operation and control of carbonization tower , carbonization technology principle and process. Based on the analysis of the influence of carbonization process on the quality of baking soda, total alkali quantity and the existing problems, this paper takes the measures to reduce consumption, makes the product quality stable to improve product competitiveness in the market of baking soda.

  3. Microcalorimetric Adsorption of Alumina Oxide Catalysts for Combination of Ethylbenzene dehydrogenation and carbon Dioxide Shift-reaction

    Institute of Scientific and Technical Information of China (English)

    GE Xin; SHEN Jian-yi


    Styrene (STY) is now produced industrially in fairly large quantities by the dehydrogenation of ethylbenzene (EB) using promoted iron oxide catalyst with superheated steam.In this case, small amount of carbon dioxide formed as a by-product was known to inhibit the catalytic activity of commercial catalyst. Recently, there have been some reports which carbon dioxide showed positive effects to promote catalytic activities on the reaction over several catalysts.In this study, we attempted to combine the dehydrogenation of EB to STY with the carbon dioxide shift-reaction. The combine reaction (EB + CO2 → STY + H2O + CO) can be considered as one of the ways of using CO2 resources and can yield simultaneously STY and Carbon oxide.Alumina oxide catalysts such as Al2O3, Na2O/Al2O3 and K2O/Al2O3 were prepared by the usual impregnation method with an aqueous solution of NaNO3 and KNO3, and then calcined at 650℃ for 5 h in a stream of air. The reaction condition is 600℃, flow of CO2 38ml/mon and space velocity (EB) 1.28h-1.

  4. Radial deformation of single-walled carbon nanotubes on quartz substrates and the resultant anomalous diameter-dependent reaction selectivity

    Institute of Scientific and Technical Information of China (English)

    Juan Yang; Yu Liu; Daqi Zhang; Xiao Wang; Ruoming Li; Yan Li


    Owing to the unique conjugated structure, the chemical-reaction selectivity of single-walled carbon nanotubes (SWNTs) has attracted great attention. By utilizing the radial deformation of SWNTs caused by the strong interactions with the quartz lattice, we achieve an anomalous diameter-dependent reaction selectivity of quartz lattice-oriented SWNTs in treatment with iodine vapor; this is distinctly different from the widely reported and well accepted higher reaction activity in small-diameter tubes compared to large-diameter tubes. The radial deformation of SWNTs on quartz substrate is verified by detailed Raman spectroscopy and mappings in both G-band and radial breathing mode. Due to the strong interaction between SWNTs and the quartz lattice, large-diameter tubes present a larger degree of radial deformation and more delocalized partial electrons are distributed at certain sidewall sites with high local curvature. It is thus easier for the carbon--carbon bonds at these high-curvature sites on large-diameter tubes to break down during reaction. This anomalous reaction activity offers a novel approach for selective removal of small-band~aD large-diameter tubes.

  5. Simulation Experiments on the Reaction of CH4-CaSO4 and Its Carbon Kinetic Isotope Fractionation

    Institute of Scientific and Technical Information of China (English)

    YueChangtao; LiShuyuan; DingKangle; ZhongNingning


    Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H,S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki(kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.

  6. Highly vibrationally excited CO generated in a low-temperature chemical reaction between carbon vapor and molecular oxygen (United States)

    Jans, E.; Frederickson, K.; Yurkovich, M.; Musci, B.; Rich, J. W.; Adamovich, I. V.


    A chemical flow reactor is used to study the vibrational population distribution of CO produced by a reaction between carbon vapor generated in an arc discharge and molecular oxygen. The results demonstrate formation of highly vibrationally excited CO, up to vibrational level v = 14, at low temperatures, T = 400-450 K, with population inversion at v = 4-7, in a collision-dominated environment, 15-20 Torr. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of reaction enthalpy. The results show feasibility of development of a new CO chemical laser using carbon vapor and oxygen as reactants.

  7. Experimental Study on Hydrocarbon Formation Due to Reactions Between Carbonates and Water or Water—Bearing Minerals in Deep Earth

    Institute of Scientific and Technical Information of China (English)

    翁克难; 汪本善; 等


    In order to investigate the mechanism of formation of abiogenetic hydrocarbons at the depth of the Earth,experimental research on reactions between carbonates and water or waterbearing minerals was carried out at the pressure of about 1GPa and the temperature range of 800-1500℃.The reactions took place in an open and nonequilibrium state.Chromatographic analyses of the gas products indicate that in the experiments there were generated CH4-dominated hydrocarbons,along with some CO2 and CO.Accordingly,we think there is no essential distinction between free-state water and hydroxy in the minerals in the process of hydrocarbon formation.This study indicates that reactions between carbonates and water or water-bearing minerals should be an important factor leading to the formation of abiogenetic hydrocarbons at the Earth's depth.

  8. Microstructure and Engineering Properties of Alkali Activated Fly Ash -as an environment friendly alternative to Portland cement

    NARCIS (Netherlands)

    Ma, Y.


    Alkali activated fly ash (AAFA), also named “geopolymer”, has emerged as a novel engineering material in the construction industry. This material is normally formed by the reaction between fly ash and aqueous hydroxide or alkali silicate solution. With proper mix design, AAFA can present comparable

  9. Role of reaction resistance in limiting carbon monoxide uptake in rabbit lungs. (United States)

    Heller, H; Schuster, K


    The contribution of reaction resistance to overall resistance to pulmonary carbon monoxide (CO) uptake [DLCO/(ThetaCO . Vc), where DLCO is lung CO diffusing capacity, ThetaCO is CO uptake conductance of erythrocytes, and Vc is pulmonary capillary blood volume] was determined in 10 anesthetized, paralyzed, and artificially ventilated rabbits. On the basis of the classical double-reciprocal equation of F. G. W. Roughton and R. E. Forster (J. Appl. Physiol. 11: 290-302, 1957), DLCO/(ThetaCO . Vc) was obtained by solving the relation DLCO/(ThetaCO . Vc) = 1 - 2/(DLNO/DLCO), where DLNO/DLCO represents the ratio between the respective single-breath diffusing capacities (DL) of nitric oxide (NO) and CO pulmonary capillary blood. The lungs of eight rabbits were inflated, starting from residual volume, by using 55 ml of indicator gas mixture (0.2% CO and 0.05% NO in nitrogen). DL values were calculated by taking the end-tidal partial pressures of CO and NO as analyzed by using a respiratory mass spectrometer. The overall value was DLCO/(ThetaCO . Vc) = 0.4 +/- 0.025 (mean +/- SD). Because of the use of O2-free indicator gas mixtures, the end-tidal O2 partial pressures were approximately 21 Torr. In one other rabbit, the application of 0.2% CO and 0.001% NO yielded DLCO/(ThetaCO . Vc) = 0.39; in the tenth rabbit, however, inspiratory volume was varied, and an identical value was found at functional residual capacity. We conclude that the contribution of reaction resistance to overall resistance to pulmonary CO uptake is independent of the inspiratory NO concentration used, including, with respect to the pertinent literature, the conclusion that in rabbits, dogs, and humans this contribution amounts to 40% when determined at functional residual capacity.

  10. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.


    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  11. Science Letters: Nitrogen doping of activated carbon loading Fe2O3 and activity in carbon-nitric oxide reaction

    Institute of Scientific and Technical Information of China (English)

    WAN Xian-kai; ZOU Xue-quan; SHI Hui-xiang; WANG Da-hui


    Nitrogen doping of activated carbon loading Fe2O3 was performed by annealing in ammonia, and the activity of the modified carbon for NO reduction was studied in the presence of oxygen. Results show that Fe2O3 enhances the amount of surface oxygen complexes and facilitates nitrogen incorporation in the carbon, especially in the form of pyridinic nitrogen. The modified carbon shows excellent activity for NO reduction in the low temperature regime (<500 ℃) because of the cooperative effect of Fe2O3 and the surface nitrogen species.

  12. Colloidal and micro-carbon spheres derived from low-temperature polymerization reactions. (United States)

    Moreno-Castilla, Carlos


    Carbon spheres (CSs) have recently attracted major interest due to their new applications, mainly in energy storage and conversion but also in hard-templating, sorption/catalysis processes, and drug delivery systems. This is attributable to their physico-chemical properties, including their tunable morphology (solid, hollow and core-shell), size, surface area/porosity, good electrical conductivity, low external surface-to-volume ratio, high packing density, enhanced mass transport, robust mechanical stability, low cytotoxicity, and excellent biocompatibility. They can be obtained from a wide variety of carbon precursors and methods. This review covers their production by carbonization of polymer spheres from low-temperature polymerization reactions, considered here as below 250°C. This is a very important method because it allows the synthesis of CSs with different morphologies and doped with other elements or chemical compounds. The preparation of polymer spheres by this technique is well documented in the literature, and the objective of this review is to summarize and give an overview of the most significant publications, proposing a novel classification based on the formation mechanism of the polymer spheres. This classification includes the following polymerization processes: emulsion polymerization and its derivatives, seeded emulsion and inverse emulsion polymerization; precipitation polymerization and its derivative, dispersion polymerization; hard-templating; spray-drying; and hydrothermal or solvothermal treatment of carbohydrates and biomass in general. This review also reports on the morphology and surface characteristics of the CSs obtained by different synthetic approaches. The final section of the review describes the current applications of these CSs, notably in energy storage (supercapacitors and rechargeable batteries) and energy conversion (fuel cells and dye-sensitized solar cells). Besides the numerous applications listed above, they are

  13. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier


    Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution and may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.

  14. A negative ion source for alkali ions

    NARCIS (Netherlands)

    Vermeer, A.; Zwol, N.A. van


    An ion source is described which delivers negative alkali ions. With this source, which consists of a duoplasmatron and a charge exchange canal with alkali vapour, negative Li, Na and K ions are produced. The oven in which alkali metals are evaporated can reach temperatures up to 575°C.

  15. Alkali binding in hydrated Portland cement paste

    NARCIS (Netherlands)

    Chen, W.; Brouwers, H.J.H.


    The alkali-binding capacity of C–S–H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C–S–H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data

  16. Carbon nanotubes-supported palladium nanoparticles for the Suzuki reaction in supercritical carbon dioxide: A facile method for the synthesis of tetrasubstituted olefins

    Institute of Scientific and Technical Information of China (English)


    A facile and efficient method for the synthesis of tetrasubstituted olefins in supercritical carbon dioxide was developed by using carbon nanotubes-supported palladium nanoparticles (Pd/CNTs) as the catalyst. Compared with common Pd/C, Pd/CNTs could more effectively catalyze the reaction of dibromo-substituted olefins with boronic acids, affording the corresponding tetrasubstituted olefins with moderate to good yields. This environmentally benign route with an easy-to-handle catalyst provides an appealing alternative to the currently available methods.

  17. Carbon nanotubes-supported palladium nanoparticles for the Suzuki reaction in supercritical carbon dioxide:A facile method for the synthesis of tetrasubstituted olefins

    Institute of Scientific and Technical Information of China (English)

    ZHOU Lei; ZHANG WeiDe; JIANG HuanFeng


    A facile and efficient method for the synthesis of tetrasubstituted olefins in supercritical carbon dioxide was developed by using carbon nanotubes-supported palladium nanoparticles (Pd/CNTs) as the cata-lyst. Compared with common Pd/C, Pd/CNTs could more effectively catalyze the reaction of di-bromo-substituted olefins with boronic acids, affording the corresponding tetrasubstituted olefins with moderate to good yields. This environmentally benign route with an easy-to-handle catalyst provides an appealing alternative to the currently available methods.

  18. Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction. (United States)

    Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui


    Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO˙ is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry.

  19. Long term stabilization of reaction center protein photochemistry by carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Magyar, Melinda; Hajdu, Kata; Szabo, Tibor; Nagy, Laszlo [Department of Medical Physics and Informatics, University of Szeged, 6720 Szeged (Hungary); Hernadi, Klara [Department of Applied and Environmental Chemistry, University of Szeged, 6720 Szeged (Hungary); Dombi, Andras [Institute of Material Sciences and Engineering, University of Szeged, 6701 Szeged (Hungary); Horvath, Endre; Magrez, Arnaud; Forro, Laszlo [Institute of Physics of Complex Matter, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne (Switzerland)


    The long term stability and the redox interaction between single walled carbon nanotubes (SWNTs) and photosynthetic reaction center proteins (RCs) purified from purple bacterium Rhodobacter sphaeroides R-26 in the SWNT/RC complex has been investigated. The binding of SWNT to RC results in an accumulation of positive (the oxidized primary electron donor, P{sup +}) and negative (semiquinone forms, Q{sup -}{sub A} and Q{sup -}{sub B}, the reduced primary and secondary quinones, respectively) charges followed by slow reorganization of the protein structure after excitation. The photochemical activity of the SWNT/RC complexes remains stable for several weeks even in dried form. In the absence of SWNT the secondary quinone activity decays quickly as a function of time after drying the RC onto a glass surface. Polarography measurements substantiate the idea that there is an electronic interaction between the RCs and SWNTs after light excitation, which was suggested earlier by optical measurements. The special electronic properties of the SWNT/protein complexes open the possibility for several applications, e.g., in microelectronics, analytics, or energy conversion and storage. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. One-step synthesis of nitrogen-iron coordinated carbon nanotube catalysts for oxygen reduction reaction (United States)

    Choi, Woongchul; Yang, Gang; Kim, Suk Lae; Liu, Peng; Sue, Hung-Jue; Yu, Choongho


    Prohibitively expensive precious metal catalysts for oxygen reduction reaction (ORR) have been one of the major hurdles in a wide use of electrochemical cells. Recent significant efforts to develop precious metal free catalysts have resulted in excellent catalytic activities. However, complicated and time-consuming synthesis processes have negated the cost benefit. Moreover, detailed analysis about catalytically active sites and the role of each element in these high-performance catalysts containing nanomaterials for large surface areas are often lacking. Here we report a facile one-step synthesis method of nitrogen-iron coordinated carbon nanotube (CNT) catalysts without precious metals. Our catalysts show excellent long-term stability and onset ORR potential comparable to those of other precious metal free catalysts, and the maximum limiting current density from our catalysts is larger than that of the Pt-based catalysts. We carry out a series of synthesis and characterization experiments with/without iron and nitrogen in CNT, and identify that the coordination of nitrogen and iron in CNT plays a key role in achieving the excellent catalytic performances. We anticipate our one-step process could be used for mass production of precious metal free electrocatalysts for a wide range of electrochemical cells including fuel cells and metal-air batteries.

  1. In situ observation of the reaction of scandium and carbon by neutron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Juarez-Arellano, Erick A., E-mail: [Institut fuer Geowissenschaften, Universitaet Frankfurt, Altenhoeferallee 1, 60438 Frankfurt a.M. (Germany); Universidad del Papaloapan, Circuito Central 200, Parque Industrial, Tuxtepec 68301 (Mexico); Winkler, Bjorn [Institut fuer Geowissenschaften, Universitaet Frankfurt, Altenhoeferallee 1, 60438 Frankfurt a.M. (Germany); Vogel, Sven C. [Los Alamos National Laboratory, Lujan Center. Mail Stop H805, Los Alamos, NM 87545 (United States); Senyshyn, Anatoliy [Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universitaet Muenchen, Lichtenbergstr. 1, D-85747 Garching (Germany); Materialwissenschaft, TU Darmstadt, Petersensstr. 23, D-64287 Darmstadt (Germany); Kammler, Daniel R. [Sandia National Laboratories, Albuquerque, NM 87185 (United States); Avalos-Borja, Miguel [CNyN, UNAM, A. Postal 2681, Ensenada, B.C. (Mexico)


    Research highlights: {yields} Exist two ScC cubic phases with B1-structure type differing in site occupancy of C. {yields} A new orthorhombic scandium carbide phase is formed at 1473(50) K. {yields} The recrystallization of alpha-Sc occurs between 1000 and 1223 K. - Abstract: The formation of scandium carbides by reaction of the elements has been investigated by in situ neutron diffraction up to 1823 K. On heating, the recrystallization of {alpha}-Sc occurs between 1000 and 1223 K. The formation of Sc{sub 2}C and ScC (NaCl-B1 type structure) phases has been detected at 1323 and 1373 K, respectively. The formation of a new orthorhombic scandium carbide phase was observed at 1473(50) K. Once the scandium carbides are formed they are stable upon heating or cooling. No other phases were detected in the present study, in which the system was always carbon saturated. The thermal expansion coefficients of all phases have been determined, they are constant throughout the temperature interval studied.

  2. Highly uniform distribution of Pt nanoparticles on N-doped hollow carbon spheres with enhanced durability for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Qiurong; Zhu, Chengzhou; Engelhard, Mark H.; Du, Dan; Lin, Yuehe


    Carbon-supported Pt nanostructures currently exhibited great potential in polymer electrolyte membrane fuel cells. Nitrogen-doped hollow carbon spheres (NHCSs) with extra low density and high specific surface area are promising carbon support for loading Pt NPs. The doped heteroatom of nitrogen could not only contribute to the active activity for the oxygen reduction reaction (ORR), but also shows a strong interaction with Pt NPs for entrapping them from dissolution/migration. This synergetic effect/interaction resulted in the uniform dispersion and strong combination of the Pt NPs on the carbon support and thus play a significant role in hindering the degradation of the catalytic activities of Pt NPs. As expected, the as-obtained Pt/NHCSs displayed improved catalytic activity and superior durability toward ORR.

  3. Nano-Scale Au Supported on Carbon Materials for the Low Temperature Water Gas Shift (WGS Reaction

    Directory of Open Access Journals (Sweden)

    Paula Sánchez


    Full Text Available Au-based catalysts supported on carbon materials with different structures such as graphite (G and fishbone type carbon nanofibers (CNF-F were prepared using two different methods (impregnation and gold-sol to be tested in the water gas shift (WGS reaction. Atomic absorption spectrometry, transmission electron microscopy (TEM, temperature-programmed oxidation (TPO, X-ray diffraction (XRD, Raman spectroscopy, elemental analyses (CNH, N2 adsorption-desorption analysis, temperature-programmed reduction (TPR and temperature-programmed decomposition were employed to characterize both the supports and catalysts. Both the crystalline nature of the carbon supports and the method of gold incorporation had a strong influence on the way in which Au particles were deposited on the carbon surface. The higher crystallinity and the smaller and well dispersed Au particle size were, the higher activity of the catalysts in the WGS reaction was noted. Finally, catalytic activity showed an important dependence on the reaction temperature and steam-to-CO molar ratio.

  4. Mechanistic aspects of the copolymerization reaction of carbon dioxide and epoxides, using a chiral salen chromium chloride catalyst. (United States)

    Darensbourg, Donald J; Yarbrough, Jason C


    The air-stable, chiral (salen)Cr(III)Cl complex (3), where H(2)salen = N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexene diamine, has been shown to be an effective catalyst for the coupling of cyclohexene oxide and carbon dioxide to afford poly(cyclohexenylene carbonate), along with a small quantity of its trans-cyclic carbonate. The thus produced polycarbonate contained >99% carbonate linkages and had a M(n) value of 8900 g/mol with a polydispersity index of 1.2 as determined by gel permeation chromatography. The turnover number (TON) and turnover frequency (TOF) values of 683 g of polym/g of Cr and 28.5 g of polym/g of Cr/h, respectively for reactions carried out at 80 degrees C and 58.5 bar pressure increased by over 3-fold upon addition of 5 equiv of the Lewis base cocatalyst, N-methyl imidazole. Although this chiral catalyst is well documented for the asymmetric ring-opening (ARO) of epoxides, in this instance the copolymer produced was completely atactic as illustrated by (13)C NMR spectroscopy. Whereas the mechanism for the (salen)Cr(III)-catalyzed ARO of epoxides displays a squared dependence on [catalyst], which presumably is true for the initiation step of the copolymerization reaction, the rate of carbonate chain growth leading to copolymer or cyclic carbonate formation is linearly dependent on [catalyst]. This was demonstrated herein by way of in situ measurements at 80 degrees C and 58.5 bar pressure. Hence, an alternative mechanism for copolymer production is operative, which is suggested to involve a concerted attack of epoxide at the axial site of the chromium(III) complex where the growing polymer chain for epoxide ring-opening resides. Preliminary investigations of this (salen)Cr(III)-catalyzed system for the coupling of propylene oxide and carbon dioxide reveal that although cyclic carbonate is the main product provided at elevated temperatures, at ambient temperature polycarbonate formation is dominant. A common reaction pathway for

  5. Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics. (United States)

    Chang, E-E; Pan, Shu-Yuan; Yang, Liuhanzi; Chen, Yi-Hung; Kim, Hyunook; Chiang, Pen-Chi


    Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO2) fixation under different operating conditions, i.e., reaction time, CO2 concentration, liquid-to-solid ratio, particle size, and CO2 flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO2 fixation capacity of 102g perkg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO2 reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO2 fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion.

  6. Behaviour of gaseous alkali compounds in coal gasification; Kaasumaisten alkaliyhdisteiden kaeyttaeytyminen kivihiilien kaasutuksessa

    Energy Technology Data Exchange (ETDEWEB)

    Nykaenen, J. [Imatran Voima Oy, Vantaa (Finland)


    In this project the behaviour of alkali compounds emitting from CO{sub 2}/O{sub 2}- and airblown gasification are studied. This research project is closely connected to an EU-project coordinated by the Delft University of Technology (DUT). In that project alkali emissions from a 1.6 MW pilot plant will be measured. The results from those measurements will be compared with the calculations performed in this LIEKKI 2 project. The equilibrium calculations show that the major gaseous alkali compounds emitting from combustion and gasification are chlorides and hydroxides. This applies both to air- and CO{sub 2}/O{sub 2}-blown processes. In all the cases studied the concentration of gaseous alkali compounds is determined mainly by the amount of chlorides. The key parameters, with respect to alkali behaviour, are the temperature of the process and chlorine content of the coal. By cooling the gases down to 600 deg C prior to a ceramic filter the alkali concentration can be kept about at 100 ppbv. In combustion, the addition of calcium carbonate increases the amount of gaseous alkali compounds by decreasing the amount of alkali sulphates. In the case of gasification the importance of limestone is negligible. The difference between air- and CO{sub 2}/O{sub 2}-blown processes, in terms of gaseous alkali emissions, is small. This is because CO{sub 2} concentration of the gas does not have a strong impact on alkali chlorides. Furthermore, the effect of CO{sub 2}/O{sub 2}-ratio of the recirculation process is negligible. (orig.)

  7. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei


    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  8. Impact of alkali salts on the kinetics and microstructural development of cementitious systems


    Mota Gassó, Berta


    Supplementary cementitious materials (SCM) lower the environmental impact of cement and concrete but react more slowly than Portland cement, which therefore limits the levels of substitution possible as reasonable early strengths are necessary. One of the main factors affecting the reaction of the SCMs is the alkalinity of the pore solution. However, alkalis do not only affect SCMs, but also the clinker phases. It is generally accepted that alkalis accelerate the hydration of Portland cement ...

  9. Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions (United States)

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

  10. 高铝粉煤灰中Al2O3与SiO2在碱溶液中的反应行为%Reaction behaviour of Al2O3 and SiO2 in high alumina coal fly ash during alkali hydrothermal process

    Institute of Scientific and Technical Information of China (English)

    蒋周青; 杨静; 马鸿文; 王乐; 马玺


    The reaction behaviours of Al2O3 and SiO2 in high alumina coal fly ash under various alkali hydrothermal conditions were studied. The means of XRD, XRF, FTIR and SEM were used to measure the mineral phase and morphology of the solid samples obtained by different alkali hydrothermal treatments as well as the leaching ratio of SiO2 to Al2O3 in alkali solution. The results showed that with the increase of the hydrothermal treating temperature from 75 to 160 °C, phillipsite-Na, zeolite A, zeolite P, and hydroxysodalite were produced sequentially while the mullite and corundum phase still remained. Zeolite P was massively formed at low-alkali concentration and the hydroxysodalite was predominantly obtained at high-alkali concentration. By the dissolution of aluminosilicate glass and the formation of zeolites together, the leaching efficiency of SiO2 can reach 42.13% with the mass ratio of Al2O3/SiO2 up to 2.19:1.%研究高铝粉煤灰中Al2O3与SiO2组分在NaOH碱液中不同水热条件下的反应行为。采用XRD、XRF、SEM、FTIR等测试方法对高铝粉煤灰碱溶液处理前后的物相组成和形貌变化进行表征,得到粉煤灰Al2O3和SiO2组分的溶出率变化规律。结果表明,高铝粉煤灰经75°C到160°C不同温度碱溶液处理后,颗粒表面硅铝玻璃相消失,依次生成钠型沸石、A型沸石、P型沸石及羟基方钠石,所含刚玉及莫来石相未被完全溶解。在低碱浓度溶液中P型沸石为主要生成相,高碱浓度下羟基方钠石为稳定的相。在铝硅玻璃体溶解和沸石相生成两种反应的共同作用下,粉煤灰中SiO2的溶出率可达42.13%,滤渣中Al2O3/SiO2质量比提高到2.19:1.

  11. Carbonation of steel slag for CO2 sequestration: Leaching of products and reaction mechanisms

    NARCIS (Netherlands)

    Huijgen, W.J.J.; Comans, R.N.J.


    Carbonation of industrial alkaline residues can be used as a CO2 sequestration technology to reduce carbon dioxide emissions. In this study, steel slag samples were carbonated to a varying extent. Leaching experiments and geochemical modeling were used to identify solubility-controlling processes of

  12. Effect of Na3PO4 on the Hydration Process of Alkali-Activated Blast Furnace Slag

    Directory of Open Access Journals (Sweden)

    Lukáš Kalina


    Full Text Available In recent years, the utilization of different non-traditional cements and composites has been increasing. Alkali-activated cementitious materials, especially those based on the alkali activation of blast furnace slag, have considerable potential for utilization in the building industry. However, alkali-slag cements exhibit very rapid setting times, which are too short in some circumstances, and these materials cannot be used for some applications. Therefore, it is necessary to find a suitable retarding admixture. It was shown that the sodium phosphate additive has a strong effect on the heat evolution during alkali activation and effectively retards the hydration reaction of alkali-activated blast furnace slag. The aim of the work is the suggestion of a reaction mechanism of retardation mainly based on Raman and X‑ray photoelectron spectroscopy.

  13. Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Chang, E-E [Department of Biochemistry, Taipei Medical University, 250 Wu-Hsing Street, Taipei City, Taiwan 110, Taiwan, ROC (China); Pan, Shu-Yuan [Graduate Institute of Environmental Engineering, National Taiwan University, 71 Chou-Shan Rd., Taipei City, Taiwan 10673, Taiwan, ROC (China); Yang, Liuhanzi [School of Environment, Tsinghua University, Haidin District, Beijing 100084 (China); Chen, Yi-Hung [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, 1, Sec. 3, Zhongxiao E. Rd., Taipei City, Taiwan 10608, Taiwan, ROC (China); Kim, Hyunook [Department of Energy and Environmental System Engineering, University of Seoul (Korea, Republic of); Chiang, Pen-Chi, E-mail: [Graduate Institute of Environmental Engineering, National Taiwan University, 71 Chou-Shan Rd., Taipei City, Taiwan 10673, Taiwan, ROC (China)


    Highlights: • Carbonation was performed using CO{sub 2}, wastewater and bottom ash in a slurry reactor. • A maximum capture capacity of 102 g CO{sub 2} per kg BA was achieved at mild conditions. • A maximum carbonation conversion of MSWI-BA was predicted to be 95% by RSM. • The CO{sub 2} emission from Bali incinerator could be expected to reduce by 6480 ton/y. • The process energy consumption per ton CO{sub 2} captured was estimated to be 180 kW h. - Abstract: Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO{sub 2}) fixation under different operating conditions, i.e., reaction time, CO{sub 2} concentration, liquid-to-solid ratio, particle size, and CO{sub 2} flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO{sub 2} fixation capacity of 102 g per kg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO{sub 2} reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO{sub 2} fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion.

  14. Carbon supported Pt-Y electrocatalysts for the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Min Ku; McGinn, Paul J. [Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN 46556 (United States)


    Carbon supported Pt{sub 3}Y (Pt{sub 3}Y/C) and PtY (PtY/C) were investigated as oxygen reduction reaction (ORR) catalysts. After synthesis via reduction by NaBH{sub 4}, the alloy catalysts exhibited 10-20% higher mass activity (mA mg{sub Pt}{sup -1}) than comparably synthesized Pt/C catalyst. The specific activity ({mu}A cm{sub Pt}{sup -2}) was 23 and 65% higher for the Pt{sub 3}Y/C and PtY/C catalysts, respectively, compared to Pt/C. After annealing at 900 C under a reducing atmosphere, Pt{sub 3}Y/C-900 and PtY/C-900 catalysts showed improved ORR activity; the Pt/C and Pt/C-900 (Pt/C catalyst annealed at 900 C) catalysts exhibited specific activities of 334 and 393 {mu}A cm{sub Pt}{sup -2}, respectively, while those of the Pt{sub 3}Y/C-900 and PtY/C-900 catalysts were 492 and 1050 {mu}A cm{sub Pt}{sup -2}, respectively. X-ray diffraction results revealed that both the Pt{sub 3}Y/C and PtY/C catalysts have a fcc Pt structure with slight Y doping. After annealing, XRD showed that more Y was incorporated into the Pt structure in the Pt{sub 3}Y/C-900 catalyst, while the PtY/C-900 catalyst remained unchanged. Although these results suggested that the high ORR activity of the PtY/C-900 catalyst did not originate from Pt-Y alloy formation, it is clear that the Pt-Y system is a promising ORR catalyst which merits further investigation. (author)

  15. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength (United States)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Wu, Guangshun; Ma, Lichun; Zhao, Min; Huang, Yudong


    Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17-10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  16. Low temperature synthesis of high quality carbon nanospheres through the chemical reactions between calcium carbide and oxalic acid

    Energy Technology Data Exchange (ETDEWEB)

    Xie Yonggui, E-mail: [State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Huang Qizhong, E-mail: [State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Huang Baiyun [State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Xie Xiangmin [Applied Chemistry Department, College of Science, Hunan Agricultural University, Changsha, Hunan 410128 (China)


    Carbon nanospheres (CNSs) were synthesized through the chemical reactions of calcium carbide and oxalic acid without using catalysts. The chemical reactions were carried out in a sealed stainless steel pressure vessel with various molar ratios at temperatures of 65-250 deg. C. The synthesized CNSs have been characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) attached to the SEM, transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. The total yield of carbonaceous materials relative to the starting material is about 4% (w/w). SEM and TEM results reveal that the percentage of CNSs is high (>95%). The CNSs that have been synthesized are roe-like spheres of relatively uniform size with diameters of 60-120 nm. The attached EDS result shows that the carbon content of CNSs reaches up to 98%.

  17. Synthesis of graphitic carbon nitride by reaction of melamine and uric acid

    Energy Technology Data Exchange (ETDEWEB)

    Dante, Roberto C., E-mail: [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martin-Ramos, Pablo, E-mail: [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Correa-Guimaraes, Adriana, E-mail: [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martin-Gil, Jesus, E-mail: [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain)


    Highlights: {yields} Graphitic carbon nitrides by CVD of melamine and uric acid on alumina. {yields} The building blocks of carbon nitrides are heptazine nuclei. {yields} Composite particles with alumina core and carbon nitride coating. - Abstract: Graphitic carbon nitrides were synthesized starting from melamine and uric acid. Uric acid was chosen because it thermally decomposes, and reacts with melamine by condensation at temperatures in the range of 400-600 deg. C. The reagents were mixed with alumina and subsequently the samples were treated in an oven under nitrogen flux. Alumina favored the deposition of the graphitic carbon nitrides layers on the exposed surface. This method can be assimilated to an in situ chemical vapor deposition (CVD). Infrared (IR) spectra, as well as X-ray diffraction (XRD) patterns, are in accordance with the formation of a graphitic carbon nitride with a structure based on heptazine blocks. These carbon nitrides exhibit poor crystallinity and a nanometric texture, as shown by transmission electron microscopy (TEM) analysis. The thermal degradation of the graphitic carbon nitride occurs through cyano group formation, and involves the bridging tertiary nitrogen and the bonded carbon, which belongs to the heptazine ring, causing the ring opening and the consequent network destruction as inferred by connecting the IR and X-ray photoelectron spectroscopy (XPS) results. This seems to be an easy and promising route to synthesize graphitic carbon nitrides. Our final material is a composite made of an alumina core covered by carbon nitride layers.

  18. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals. (United States)

    Khaled, Fethi; Giri, Binod Raj; Szőri, Milán; Mai, Tam V-T; Huynh, Lam K; Farooq, Aamir


    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  19. Protective effect of application of carbon nanoparticles in thyroid cancer surgery and evaluation of inflammatory stress reaction degree

    Institute of Scientific and Technical Information of China (English)

    Qing-Sheng Zheng; Jun-Zheng Li; Wei-Xiong Hong; Jiao-Yuan Xu; Si-Yi Zhang


    Objective:To study the protective effect of application of carbon nanoparticles in thyroid cancer surgery and its influence on inflammatory stress reaction degree.Methods:Patients who received thyroid cancer surgery in our hospital from June 2013 to June 2014 were chosen for study and randomly divided into conventional group and nano-carbon group. Then contents of thyroid cancer related malignant molecules, pro-inflammation cytokines and inflammation inhibiting factors in serum were detected.Results:(1) Malignant molecules: compared with conventional group, mRNA levels of Wip1, gal-3, SATB1, LSD1, GDF-15 and TBX2 in serum of nano-carbon group were lower; (2) Inflammation inhibiting factors: compared with conventional group, serum MFG-E8 and Omentin-1 levels of nano-carbon group were higher; (3) Pro-inflammation cytokines: compared with conventional group, serum MIP-1, SGK-1 and β-EP levels of nano-carbon group were lower.Conclusion: Application of carbon nanoparticles in thyroid cancer surgery is helpful to reduce operative damage to thyroid tissue, prevent release of malignant biological molecules into bloodstream and relieve inflammatory response; it’s an ideal surgical method for thyroid cancer.

  20. Surface-nitrogen-rich ordered mesoporous carbon as an efficient metal-free electrocatalyst for oxygen reduction reaction (United States)

    Xiao, Chunhui; Chen, Xu; Fan, Zhaoyang; Liang, Jin; Zhang, Bo; Ding, Shujiang


    Exploring efficient metal-free electrocatalysts for oxygen reduction reactions (ORR) will have a great impact on the field of fuel cells and metal-air batteries. In this paper, we report a simple and efficient routine to coat ordered mesoporous carbon (CMK-3) with nitrogen-doped carbon via pyrolysis of the surface-self-polymerized polydopamine. The optimized CMK-3 catalyst with a coating of nitrogen-doped carbon demonstrates excellent electrocatalytic activity towards ORR in alkaline media. The coating procedure under optimized conditions lowers the ORR half-wave-potential by 80 mV, giving a genuine metal-free catalyst with an onset ORR potential of 0.96 V (vs reversible hydrogen electrode (RHE)) and half-wave potential of 0.83 V (vs RHE) in 0.1 M KOH, which is much better than other carbon material-based catalysts (such as carbon nanotubes and their composites). The performance of this surface-nitrogen-rich CMK-3 catalyst is also superior to that of N-doped ordered mesoporous carbon synthesized by means of the ‘nanocasting’ technique. Furthermore, the as-prepared catalyst performs comparably in terms of activity, superior durability, and higher tolerance to methanol compared with commercially available Pt/C.

  1. Reaction pathway led by silicate structure transformation on decomposition of CaSiO3 in alkali fusion process using NaOH%NaOH碱熔分解CaSiO 3过程中导致硅酸盐结构转变的反应路径

    Institute of Scientific and Technical Information of China (English)

    赵昌明; 王国承; 李胜利; 艾新港; 王子睿; 翟玉春


    以NaSiO 3·9H 2 O和CaCl 2为原料,通过化学沉积法合成链状硅酸盐(CaSiO 3)。采用拉曼光谱、X射线衍射和红外光谱研究其在NaOH碱熔过程中的分解机制。结果表明,CaSiO 3在碱熔过程中链状结构的硅氧四面体结构逐渐断裂、转变生成岛状结构的硅氧四面体。CaSiO3分解过程中同时生成3种中间体:Ca2SiO4, Na2CaSiO4和Na2SiO3,最终产物是Ca(OH)2和 Na4SiO4。因此,CaSiO3在NaOH碱熔融反应过程中存在两条反应途径,分别以离子交换和硅酸盐骨架结构改变为主要形式,碱熔过程中硅酸盐结构的变化贯穿于整个反应过程。%The mechanism of decomposition of calcium inosilicate (CaSiO3) synthesized through chemical deposition method using analytical reagent NaSiO3∙9H2O and CaCl2 during the alkali fusion process using NaOH was investigated by Raman spectroscopy in situ, X-ray diffraction and Fourier transform infrared spectrometer (FTIR). The results show that the tetrahedral silica chains within CaSiO3 are gradually disrupted and transformed into nesosilicate with the isolated SiO4 tetrahedra at the beginning of the alkali fusion process. The three intermediates including Ca2SiO4, Na2CaSiO4 and Na2SiO3 appear simultaneously in the decomposition of CaSiO3, while the final products are Ca(OH)2 and Na4SiO4. It can be concluded that there exist two reaction pathways in the alkali fusion process of CaSiO3: one is ion exchange, the other is in the main form of the framework structure change of silicate. The reaction pathway is led by silicate structure transformation in the alkali fusion process.

  2. Biodegradation of Leonardite by an alkali-producing bacterial community and characterization of the degraded products. (United States)

    Gao, Tong-Guo; Jiang, Feng; Yang, Jin-Shui; Li, Bao-Zhen; Yuan, Hong-Li


    In this study, three bacterial communities were obtained from 12 Leonardite samples with the aim of identifying a clean, effective, and economic technique for the dissolution of Leonardite, a type of low-grade coal, in the production of humic acid (HA). The biodegradation ability and characteristics of the degraded products of the most effective bacterial community (MCSL-2), which degraded 50% of the Leonardite within 21 days, were further investigated. Analyses of elemental composition, (13)C NMR, and Fourier transform infrared revealed that the contents of C, O, and aliphatic carbon were similar in biodegraded humic acid (bHA) and chemically (alkali) extracted humic acid (cHA). However, the N and carboxyl carbon contents of bHA was higher than that of cHA. Furthermore, a positive correlation was identified between the degradation efficiency and the increasing pH of the culture medium, while increases of manganese peroxidase and esterase activities were also observed. These data demonstrated that both alkali production and enzyme reactions were involved in Leonardite solubilization by MCSL-2, although the former mechanism predominated. No fungus was observed by microscopy. Only four bacterial phylotypes were recognized, and Bacillus licheniformis-related bacteria were identified as the main group in MCSL-2 by analysis of amplified 16S rRNA genes, thus demonstrating that Leonardite degradation ability has a limited distribution in bacteria. Hormone-like bioactivities of bHA were also detected. In this study, a bacterial community capable of Leonardite degradation was identified and the products characterized. These data implicate the use of such bacteria for the exploitation of Leonardite as a biofertilizer.

  3. Positron-alkali atom scattering (United States)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.


    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  4. Electrocatalytic oxygen evolution reaction at a FeNi composite on a carbon nanofiber matrix in alkaline media

    Institute of Scientific and Technical Information of China (English)

    Xianghua An; Dongyoon Shin; Joey D. Ocon; Jae Kwang Lee; Young-il Son; Jaeyoung Lee


    Non-noble metals such as Fe and Ni have comparable electrocatalytic activity and stability to that of Ir and Ru in an oxygen evolution reaction (OER). In this study, we synthesized carbon nanofibers with embedded FeNi composites (FeNi-CNFs) as OER electrocatalysts by a facile route comprising electrospinning and the pyrolysis of a mixture of metal precursors and a polymer solution. FeNi-CNFs demonstrated catalytic activity and stability that were better than that of 20 wt%Ir on Vulcan carbon black in oxidizing water to produce oxygen in an alkaline media. Physicochemical and electrochemical characterization revealed that Fe and Ni had synergistic roles that enhanced OER activity by the uniform formation and widening of pores in the carbon structure, while the CNF matrix also contributed to the increased stability of the catalyst.

  5. Potassium-decorated active carbon supported Co-Mo-based catalyst for water-gas shift reaction

    Institute of Scientific and Technical Information of China (English)

    Yixin Lian; RuiFen Xiao; Weiping Fang; Yiquan Yang


    The effect of potassium-decoration was studied on the activity of water-gas shift(WGS)reaction over the Co-Mo-based catalysts supported on active carbon(AC),which was prepared by incipient wetness co-impregnation method.The decoration of potassium on active carbon in advance enhances the activities of the CoMo-K/AC catalysts for WGS reaction.Highest activity(about 92% conversion)was obtained at250 ℃ for the catalyst with an optimum K2O/AC weight ratio in the range from 0.12 to 0.15.The catalysts were characterized by TPR and EPR,and the results show that activated carbon decorated with potassium makes Co-Mo species highly dispersed,and thus easily reduced and sulfurized.XRD results show that an appropriate content of potassium-decoration on active carbon supports may favors the formation of highly dispersed Co9Ss-type structures which are situated on the edge or a site in contact with MoS2,K-Mo-O-S,Mo-S-K phase.Those active species are responsible for the high activity of CoMo-K/AC catalysts.

  6. First-principles study of ternary graphite compounds cointercalated with alkali atoms (Li, Na, and K) and alkylamines towards alkali ion battery applications (United States)

    Ri, Gum-Chol; Yu, Chol-Jun; Kim, Jin-Song; Hong, Song-Nam; Jong, Un-Gi; Ri, Mun-Hyok


    First-principles calculations were carried out to investigate the structural, energetic, and electronic properties of ternary graphite compounds cointercalated with alkali atoms (AM = Li, Na, and K) and normal alkylamine molecules (nCx; x = 1, 2, 3, 4), denoted as AM-nCx-GICs. From the optimization of the orthorhombic unit cells for the crystalline compounds, it was found that, with the increase in the atomic number of alkali atoms, the layer separations decrease in contrast to AM-GICs, while the bond lengths between alkali atoms and graphene layer, and nitrogen atom of alkylamine increase. The calculated formation energies and interlayer binding energies of AM-nC3-GICs indicate that the compounds is increasingly stabilized from Li to K, and the energy barriers for migration of alkali atoms suggest that alkali cation with larger ionic radius diffuses more smoothly in graphite, being similar to AM-GICs. Through the analysis of electronic properties, it was established that more extent of electronic charge is transferred from more electropositive alkali atom to the carbon ring of graphene layer, and the hybridization of valence electron orbitals between alkylamine molecules and graphene layer is occurred.

  7. The Durability and Performance of Short Fibers for a Newly Developed Alkali-Activated Binder

    Directory of Open Access Journals (Sweden)

    Henrik Funke


    Full Text Available This study reports the development of a fiber-reinforced alkali-activated binder (FRAAB with an emphasis on the performance and the durability of the fibers in the alkaline alkali-activated binder (AAB-matrix. For the development of the matrix, the reactive components granulated slag and coal fly ash were used, which were alkali-activated with a mixture of sodium hydroxide (2–10 mol/L and an aqueous sodium silicate solution (SiO2/Na2O molar ratio: 2.1 at ambient temperature. For the reinforcement of the matrix integral fibers of alkali-resistant glass (AR-glass, E-glass, basalt, and carbon with a fiber volume content of 0.5% were used. By the integration of these short fibers, the three-point bending tensile strength of the AAB increased strikingly from 4.6 MPa (no fibers up to 5.7 MPa (carbon after one day. As a result of the investigations of the alkali resistance, the AR-glass and the carbon fibers showed the highest durability of all fibers in the FRAAB-matrix. In contrast to that, the weight loss of E-glass and basalt fibers was significant under the alkaline condition. According to these results, only the AR-glass and the carbon fibers reveal sufficient durability in the alkaline AAB-matrix.

  8. Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution II: Solvent Coordinate-Dependent Reaction Path. (United States)

    Daschakraborty, Snehasis; Kiefer, Philip M; Miller, Yifat; Motro, Yair; Pines, Dina; Pines, Ehud; Hynes, James T


    The protonation of methylamine base CH3NH2 by carbonic acid H2CO3 within a hydrogen (H)-bonded complex in aqueous solution was studied via Car-Parrinello dynamics in the preceding paper (Daschakraborty, S.; Kiefer, P. M.; Miller, Y.; Motro, Y.; Pines, D.; Pines, E.; Hynes, J. T. J. Phys. Chem. B 2016, DOI: 10.1021/acs.jpcb.5b12742). Here some important further details of the reaction path are presented, with specific emphasis on the water solvent's role. The overall reaction is barrierless and very rapid, on an ∼100 fs time scale, with the proton transfer (PT) event itself being very sudden (water solvent changes little until the actual PT occurrence; this results from the very strong driving force for the reaction, as indicated by the very favorable acid-protonated base ΔpKa difference. Further solvent rearrangement follows immediately the sudden PT's production of an incipient contact ion pair, stabilizing it by establishment of equilibrium solvation. The solvent water's short time scale ∼120 fs response to the incipient ion pair formation is primarily associated with librational modes and H-bond compression of water molecules around the carboxylate anion and the protonated base. This is consistent with this stabilization involving significant increase in H-bonding of hydration shell waters to the negatively charged carboxylate group oxygens' (especially the former H2CO3 donor oxygen) and the nitrogen of the positively charged protonated base's NH3(+).

  9. Domino Michael-Michael and Aldol-Aldol Reactions: Diastereoselective Synthesis of Functionalized Cyclohexanone Derivatives Containing Quaternary Carbon Center. (United States)

    Ghorai, Manas K; Halder, Sandipan; Das, Subhomoy


    A simple strategy for the synthesis of highly functionalized cyclohexanone derivatives containing an all-carbon quaternary center from α-(aryl/alkyl)methylidene-β-keto esters or β-diketones via a K-enolate mediated domino Michael-Michael reaction sequence with moderate to good yield and excellent diastereoselectivity (de > 99%) is described. Interestingly, Li-base mediated reaction of α-arylmethylidene-β-diketones affords functionalized 3,5-dihydroxy cyclohexane derivatives as the kinetically controlled products via a domino aldol-aldol reaction sequence with excellent diastereoselectivity. Li-enolates of the β-keto esters or β-diketones undergo facile domino Michael-Michael reaction with nitro-olefins to afford the corresponding nitrocyclohexane derivatives in good yields and excellent diastereoselectivity (de > 99%). The formation of the products and the observed stereoselectivity were explained by plausible mechanisms and supported by extensive computational study. An asymmetric version of the protocol was explored with (L)-menthol derived nonracemic substrates, and the corresponding nonracemic cyclohexanone derivatives containing an all-carbon quaternary center were obtained with excellent stereoselectivity (de, ee > 99%).

  10. Transition metal/nitrogen dual-doped mesoporous graphene-like carbon nanosheets for the oxygen reduction and evolution reactions (United States)

    Liu, Xiaobo; Amiinu, Ibrahim Saana; Liu, Shaojun; Cheng, Kun; Mu, Shichun


    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures.The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures. Electronic supplementary information (ESI) available: The XPS fitted results, SEM and TEM images, the K-L equation, and some of the electrochemical

  11. Carbon doped molybdenum disulfide nanosheets stabilized on graphene for the hydrogen evolution reaction with high electrocatalytic ability (United States)

    Li, Yong; Wang, Jiao; Tian, Xike; Ma, Longlong; Dai, Chu; Yang, Chao; Zhou, Zhaoxin


    Fabricating a cost effective hydrogen evolution reaction catalyst without using precious metal elements is in crucial demand for environmentally-benign energy production. In this work, the thin and edge-rich molybdenum disulfide nanosheets, with carbon doped in the interlayers and decorated on graphene, were developed by a facile solvothermal process. The as-synthesized nanohybrids exhibited high catalytic ability for the hydrogen evolution electrochemical reaction with an onset overpotential of 0.165 mV and a Tafel slope of 46 mV dec-1. Furthermore, the prepared nanohybrids also showed better durability and stability. Our work may lead to a potential method for in situ production of metal carbide-sulphur hybrid nanomaterials with promising applications for the hydrogen evolution reaction.Fabricating a cost effective hydrogen evolution reaction catalyst without using precious metal elements is in crucial demand for environmentally-benign energy production. In this work, the thin and edge-rich molybdenum disulfide nanosheets, with carbon doped in the interlayers and decorated on graphene, were developed by a facile solvothermal process. The as-synthesized nanohybrids exhibited high catalytic ability for the hydrogen evolution electrochemical reaction with an onset overpotential of 0.165 mV and a Tafel slope of 46 mV dec-1. Furthermore, the prepared nanohybrids also showed better durability and stability. Our work may lead to a potential method for in situ production of metal carbide-sulphur hybrid nanomaterials with promising applications for the hydrogen evolution reaction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07370g

  12. Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction (United States)

    Ahmed, Nesreen S.; Menzel, Robert; Wang, Yifan; Garcia-Gallastegui, Ainara; Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N.; Mokhtar, Mohamed


    Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.

  13. Penetration of alkali atoms throughout a graphene membrane: theoretical modeling. (United States)

    Boukhvalov, D W; Virojanadara, C


    Theoretical studies of penetration of various alkali atoms (Li, Na, Rb, Cs) throughout a graphene membrane grown on a silicon carbide substrate are reported and compared with recent experimental results. Results of first principles modeling demonstrate a rather low (about 0.8 eV) energy barrier for the formation of temporary defects in the carbon layer required for the penetration of Li at a high concentration of adatoms, a higher (about 2 eV) barrier for Na, and barriers above 4 eV for Rb and Cs. Experiments prove migration of lithium adatoms from the graphene surface to the buffer layer and SiC substrate at room temperature, sodium at 100 °C and impenetrability of the graphene membrane for Rb and Cs. Differences between epitaxial and free-standing graphene for the penetration of alkali ions are also discussed.

  14. Examining the role of carbonation and temperature on water swallowing performance: a swallowing reaction-time study. (United States)

    Michou, Emilia; Mastan, Aliya; Ahmed, Saira; Mistry, Satish; Hamdy, Shaheen


    Various therapeutic approaches for dysphagia management are based on modifications of bolus properties to change swallowing biomechanics and increase swallowing safety. Limited evidence exists for the effects of carbonation and bolus temperature on swallowing behavior. Here, we investigated the effects of carbonation and temperature on swallowing behavior using a novel automated and complex swallowing reaction time task via pressure signal recordings in the hypopharynx. Healthy participants (n = 39, 27.7±5 years old) were randomized in two different experiments and asked to perform 10 normal-paced swallows, 10 fast-paced swallows, and 10 challenged swallows within a predetermined time-window of carbonated versus still water (experiment 1) and of cold (4 °C) versus hot (45 °C) versus room temperature (21 °C) water (experiment 2). Quantitative measurements of latencies and percentage of successful challenged swallows were collected and analyzed nonparametrically. An increase in successfully performed challenged swallowing task was observed with carbonated water versus still water (P = 0.021), whereas only cold water shortened the latencies of normally paced swallows compared with room (P = 0.001) and hot (P = 0.004) temperatures. Therefore, it appears that chemothermal stimulation with carbonation and cold are most effective at modulating water swallowing, which in part is likely to be driven by central swallowing afferent activity.

  15. Oxygen reduction activity of carbon fibers cathode, and application for current generation from the NAD+ and NADH recycling reaction

    Directory of Open Access Journals (Sweden)

    H. Maeda


    Full Text Available Carbon fibers treated at 700 oC for 10 min were found to have O2 reduction activity when being used as a cathode. The special type of partition combined with both cationic and anionic exchange membranes was applied between anode cell and cathode cell in order to use a highly acidic solution such as 0.5 M H2SO4 as an electrolyte of the cathode cell for increasing the efficiency of O2 reduction activity. The current generation from NAD+ and NADH recycling system combined with D-gluconolactone production from 500 mg of D-glucose was performed by applying only carbon fibers for both anode and cathode. The total current volume obtained was 81.4 mAh during the reaction for 10 h, and the current efficiency was 93%. One gram of carbon fibers was pressed with Nafion paste on a piece of carbon paper(area : 50 mm×50mm with heating to prepare the cathode, and this construct was combined with conventional fuel cell. The power density was 3.6 mW/cm2, and the total power volume was calculated to be 90 mW per 1 g of carbon fibers.

  16. Performance characterization of rigid polyurethane foam with refined alkali lignin and modified alkali lignin

    Institute of Scientific and Technical Information of China (English)

    LIU Zhi-ming; YU Fei; FANG Gui-zhen; YANG Hui-jun


    The two kinds of rigid polyurethane (PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.

  17. Heterometallic aluminates: alkali metals trapped by an aluminium aryloxide claw. (United States)

    Muñoz, M Teresa; Cuenca, Tomás; Mosquera, Marta E G


    A series of heterometallic aluminium-alkali metal species [AlMMe2{2,6-(MeO)2C6H3O}2]n have been isolated for lithium, sodium and potassium. These compounds can be generated by the reaction of [AlMe2{2,6-(MeO)2C6H3O}]2 with the metallated phenol [M{2,6-(MeO)2C6H3O}]n or through the reaction of the mixture of AlMe3 and the appropriate alkali metal alkyl base with two equivalents of 2,6-dimethoxyphenol. In the heterometallic species obtained, the {AlMe2{2,6-(MeO)2C6H3O}2}(-) moiety is observed and could be described as a claw which fixes the alkali ion by the phenoxide oxygen atoms while the methoxy groups help to stabilize their coordination sphere. All compounds have been characterized by NMR spectroscopy and X-ray diffraction methods. Catalytic studies reveal that these compounds are active in ring-opening polymerization of L-lactide.

  18. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide (United States)

    Hill Bembenic, Meredith A.

    collected solids from the CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C-NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were obtained when using CO according to GC/MS analysis. Therefore, reactions with CO were completed that varied the initial reaction pressure (300, 500 and 800 psi) in order to elucidate the effects of CO pressure. Similar conversion (≈54--58%) and DCM-soluble liquid product yields (≈53--62%) were obtained for the different pressure reactions, but the reactions with an initial pressure of 500 psi had the greatest change in aromaticity from the unreacted lignin. Additional reactions between Organosolv lignin and H2O with CO (initial pressure of 500 psi) were conducted where the reaction time was varied (15, 30 and 60 min.) to determine the effect of reaction time. Longer reaction time (60 min.) appeared to inhibit conversion to low molecular weight compounds (i.e., conversion and DCM-soluble yields were lower at ≈53% and ≈28%, respectively). Solid state 13C-NMR of collected residues also showed that there are losses in carbons representative of both guaiacyl and syringyl components as reaction time increases, which may indicate that methoxy groups are being cleaved or the products are reacting with each other (i.e., repolymerization) to form high molecular weight compounds as reaction time is increased. The role of H2O and the gases during the baseline reactions and the expanded CO reactions is not intuitive based on the results, so reactions with lignin model compounds (i.e., aromatic aldehydes represented by vanillin and syringaldehyde, aromatic ketones represented by acetovanillone and acetosyringone, and aromatic ethers represented by dibenzyl ether and 2-phenethyl phenyl ether) were completed to study this. From these results, the suggested reaction pathway of Organosolv lignin reactions in subcritical H2O with and without

  19. Tailoring Synthesis Conditions of Carbon Xerogels towards Their Utilization as Pt-Catalyst Supports for Oxygen Reduction Reaction (ORR

    Directory of Open Access Journals (Sweden)

    María Jesús Lázaro


    Full Text Available Carbon xerogels characterized by different textural, structural and chemical properties were synthesized and used as supports for Pt catalysts for the application in polymer electrolyte fuel cells. Synthesis conditions were varied in order to synthesize carbon xerogels following the sol-gel method. These included the reactants ratio (precursor/formaldehyde, the catalyst concentration (precursor/catalyst ratio and type (basic and acid, the precursor type (resorcinol and pyrogallol and the solvent (aqueous or acetone based. Stoichiometric mixtures of resorcinol and formaldehyde yielded well polymerized gels and highly developed structures. Slow gelation, favored by the presence of acetone as solvent in the sol and low catalyst concentration, resulted in higher polymerization extent with a highly mesoporous or even macroporous texture and more ordered structure, as evidenced by XPS and Raman spectroscopy. Small Pt particles of ca. 3.5 nm were obtained by using carbon xerogels characterized by an ordered surface structure. The specific activity towards the oxygen reduction reaction, i.e., the limiting catalytic process in low temperature fuel cells, is significantly favored by highly ordered carbon xerogels due to a metal-support enhanced interaction. Nevertheless, surface defects favor the distribution of the metallic particles on the surface of carbon, which in the end influences the effectiveness of the catalyst. Accelerated degradation tests were conducted to evaluate catalyst stability under potential cycling conditions. The observed decay of performance was considerably lower for the catalysts based on ordered carbon xerogels stabilizing Pt particles in a higher extent than the other xerogels and the commercial carbon black support.

  20. Mechanistic and kinetic analysis of the oxidative dehydrogenation of ethane via novel supported alkali chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.; Veen, A.C. van; Lercher, J.A. [Technische Universitaet Muenchen (Germany). Catalysis Research Center


    The oxidative dehydrogenation of ethane over advanced catalysts is promising to selectively produce ethylene, an essential building block for the chemical industry. In this way, ethane from shale gas can be efficiently valorized. Supported alkali chloride catalysts are investigated in this work. Essential feature of those materials is the presence of a solid core (magnesium oxide in part doped with Dy{sub 2}O{sub 3}) covered under reaction conditions with a molten alkali chloride shell. It is shown that especially the lowered melting point of eutectic mixtures of LiCl with other alkali/alkaline earth metals is the key to taylor highly efficient materials. Elucidating the ODH reaction mechanism is essential to understand the reactivity of this novel catalyst class and provides the basis for improving performances. Information about elementary steps and the rate determining step were extracted from kinetic measurements, both in steady state and in transient configuration. Furthermore, isotopic labelling studies were performed, i.e. SSITKA studies and temperature programmed isotopic exchange experiments. Step experiments showed a significant oxygen uptake by the catalysts. Retained oxygen reacted quantitatively with ethane at nearly 100% selectivity to ethylene and conversion rates were comparable with rates observed during steady state operation. Thus, chemically bound oxygen in the melt is the active and selective intermediate in the ODH. Therefore, it is required to consider an intermediate and the activation is concluded to relate to the oxygen dissociation. The total concentration of stored oxygen can be correlated to the steady-state activity, while the viscosity of the melts mainly influences the selectivity towards ethene. Properties of the solid core impact on the catalyst efficiency suggesting that the oxygen species forms at the interface between support and overlayer. The quantity of retained oxygen additionally depends on the properties of the chloride

  1. Nitrogen-Doped Carbon Nanoparticle-Carbon Nanofiber Composite as an Efficient Metal-Free Cathode Catalyst for Oxygen Reduction Reaction. (United States)

    Panomsuwan, Gasidit; Saito, Nagahiro; Ishizaki, Takahiro


    Metal-free nitrogen-doped carbon materials are currently considered at the forefront of potential alternative cathode catalysts for the oxygen reduction reaction (ORR) in fuel cell technology. Despite numerous efforts in this area over the past decade, rational design and development of a new catalyst system based on nitrogen-doped carbon materials via an innovative approach still present intriguing challenges in ORR catalysis research. Herein, a new kind of nitrogen-doped carbon nanoparticle-carbon nanofiber (NCNP-CNF) composite with highly efficient and stable ORR catalytic activity has been developed via a new approach assisted by a solution plasma process. The integration of NCNPs and CNFs by the solution plasma process can lead to a unique morphological feature and modify physicochemical properties. The NCNP-CNF composite exhibits a significantly enhanced ORR activity through a dominant four-electron pathway in an alkaline solution. The enhancement in ORR activity of NCNP-CNF composite can be attributed to the synergistic effects of good electron transport from highly graphitized CNFs as well as abundance of exposed catalytic sites and meso/macroporosity from NCNPs. More importantly, NCNP-CNF composite reveals excellent long-term durability and high tolerance to methanol crossover compared with those of a commercial 20 wt % supported on Vulcan XC-72. We expect that NCNP-CNF composite prepared by this synthetic approach can be a promising metal-free cathode catalyst candidate for ORR in fuel cells and metal-air batteries.

  2. Facile Precursor for Synthesis of Silver Nanoparticles Using Alkali Treated Maize Starch (United States)

    El-Rafie, M. H.; Ahmed, Hanan B.; Zahran, M. K.


    Silver nanoparticles were prepared by using alkali treated maize starch which plays a dual role as reducer for AgNO3 and stabilizer for the produced AgNPs. The redox reaction which takes a place between AgNO3 and alkali treated starch was followed up and controlled in order to obtain spherical shaped silver nanoparticles with mean size 4–6 nm. The redox potentials confirmed the principle role of alkali treatment in increasing the reducibility of starch macromolecules. The measurements of reducing sugars at the end of reaction using dinitrosalicylic acid reagent (DNS) were carried out in order to control the chemical reduction reaction. The UV/Vis spectra show that an absorption peak, occurring due to surface plasmon resonance (SPR), exists at 410 nm, which is characteristic to yellow color of silver nanoparticles solution. The samples have been characterized by transmission electron microscopy (TEM), which reveal the nanonature of the particles. PMID:27433508

  3. Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (V) Screening Catalysts and Optimizing Synthesis Conditions

    Institute of Scientific and Technical Information of China (English)

    张光旭; 吴元欣; 马沛生; 田崎峰; 吴广文; 李定或; 王存文


    Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was La0.62Pb0.38MnO3 and the average diameter could be about 25.4 nm. The optimum conditions for synthesis of DPC with Pd/LaxPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catMyst/phenol mass ratio 1 to 50, pressure 4.5 MPa,volume concentration of O2 25%, reaction temperature 60° and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

  4. Flow characteristics and reaction properties of carbon dioxide in microtubules and porous media

    Institute of Scientific and Technical Information of China (English)

    ZHAO RenBao; YUE XiangAn; WU Ya Hong; XU ShaoLiang; WANG Fei; HOU YongLi


    Carbon dioxide reacts with porous media while flowing through them enhancing their permeability. Its flow behavior as well as the permeability enhancement effects were studied in synthetic cores, natural cores and microtubes with an inner diameter of 5 μm. The results show that the permeability of H2O-saturated cores (containing carbonate ingredients) was enhanced by increasing the injection volume of a CO2-H2O solution. This enhancement is attributable to carbon dioxide's corrosion, which is justified by SEM scanning. The same phenomenon occurs with a CO2-H2O solution in microtubes, but for a different reason. The gas flow velocity of carbon dioxide in microtubes was approximately 100% aster than that of nitrogen because of the scale and the squeezing effects. Carbon dioxide molecules dissolved in water accelerate the diffusion rate of water molecules within the boundary layer, which in turn diminishes the thickness of the water film and enlarges the effective pore size. This flow behavior facilitates the injection of carbon dioxide into low-permeability reservoirs for oil-displacement and formation energy buildup purposes. This behavior also increases the potential for carbon dioxide channeling or release from the formation.

  5. Synthesis of Diethyl Oxalate by a Coupling-Regeneration Reaction of Carbon Monoxide

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Baowei Wang; Xinbin Ma


    This article describes a process for the synthesis of diethyl oxalate by a coupling reaction ofcarbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism ofthe coupling and regeneration reaction are also discussed. This paper presents the results of a scale-uptest of the catalyst and the process based on an a priori computer simulation.

  6. Hairy foam : thin layers of carbon nanofibers as catalyst support for liquid phase reactions

    NARCIS (Netherlands)

    Chinthaginjala, Jitendra Kumar


    Catalytic multiphase reactors are at the heart of many chemical industries. They allow efficient contact between gas and/or liquid reactant phases with solid catalysts increasing reaction rates. In practice, the higher reaction rates can be taken advantage of only under the condition that the transf

  7. Efficient Cycloaddition Reaction of Carbon Dioxide with Epoxide by Rhodamine Based Catalyst Under 1 atm Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Qing; Luo, Huadong; Cao, Di; Zhang, Haibo; Wang, Wenjing; Zhou, Xiaohai [Wuhan University, Wuhan (China)


    Rhodamine B (RhB) and rhodamine 6G (Rh6G) were employed as catalysts for the synthesis of cyclic carbonate from carbon dioxide and epoxide. It turned out that the catalytic activity of Rh6G was nearly 29 times higher than that of RhB at 1 atm pressure, 90 .deg. C. Furthermore, the catalytic efficiency of RhB and Rh6G was greatly enhanced with triethylamine as co-catalyst. Under the optimized conditions, the best isolated yield (93%) of cyclic carbonate was achieved without organic solvent and metal component

  8. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

    Directory of Open Access Journals (Sweden)

    K Huang

    Full Text Available Novel graphite-molybdenum carbide nanocomposites (G-Mo2C are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV, rotating disk electrode (RDE and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

  9. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction. (United States)

    Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M


    Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

  10. Nitrogen-doped carbon-embedded TiO2 nanofibers as promising oxygen reduction reaction electrocatalysts (United States)

    Hassen, D.; Shenashen, M. A.; El-Safty, S. A.; Selim, M. M.; Isago, H.; Elmarakbi, A.; El-Safty, A.; Yamaguchi, H.


    The development of inexpensive and effective electrocatalysts for oxygen reduction reaction (ORR) as a substitute for commercial Pt/C catalyst is an important issue in fuel cells. In this paper, we report on novel fabrication of self-supported nitrogen-doped carbon-supported titanium nanofibers (Nsbnd TiO2@C) and carbon-supported titanium (TiO2@C) electrocatalysts via a facile electrospinning route. The nitrogen atom integrates physically and homogenously into the entire carbon-titanium structure. We demonstrate the catalytic performance of Nsbnd TiO2@C and TiO2@C for ORR under alkaline conditions in comparison with Pt/C catalyst. The Nsbnd TiO2@C catalyst shows excellent ORR reactivity and durability. Interestingly, among all the catalysts used in this ORR, Nsbnd TiO2@C-0.75 exhibits remarkable competitive oxygen reduction activity in terms of current density and onset potential, as well as superior methanol tolerance. Such tolerance attributes to maximizing the diffusion of trigger pulse electrons during catalytic reactions because of enhanced electronic features. Results indicate that our fabrication strategy can provide an opportunity to produce a simple, efficient, cost-effective, and promising ORR electrocatalyst for practical applications in energy conversion and storage technologies.

  11. Synthesis and infrared spectra of alkaline earth metal carbonates formed by the reaction of metal salts with urea at high temperature

    Indian Academy of Sciences (India)

    S M Teleb; D El-Sayed Nassr; E M Nour


    The metal carbonate, MCO3 (M = Ca, Sr and Ba), was synthesized by a novel method of reacting aqueous solution of each of Ca2+, Sr2+ and Ba2+ salts with urea at high temperature, ∼ 80°C. The reaction products were characterized through elemental analysis and infrared spectra. The infrared spectra of the products are the same as those of the corresponding commercially obtained carbonates. A general reaction describing the formation of MCO3 is proposed.

  12. Carbon-supported palladium and ruthenium nanoparticles: application as catalysts in alcohol oxidation, cross-coupling and hydrogenation reactions. (United States)

    García-Suárez, Eduardo J; Lara, Patricia; García, Ana B; Philippot, Karine


    In the last fifteen-years, the application of metal nanoparticles as catalysts in organic synthesis has received a renewed interest. Therefore, much attention is currently being paid to the synthesis of metal nanoparticles in order to achieve the control of their characteristics in terms of size, shape and surface chemistry. Besides this, the recyclability as well as the recovery from the reaction medium still remain the major drawbacks to widespread the use of nanoparticles in catalysis. To overcome these problems, the immobilization of metal nanoparticles on solid supports appears as a promising alternative. In that context, carbon materials offer several advantages as solid supports such as availability, relatively low cost, high mechanical strength, chemical stability, and a pore structure along with an attractive surface chemistry which allows easy modifications, such as its functionalization, to suit the nanoparticles immobilization needs. Among the transition metals Palladium and Ruthenium are widely employed as efficient catalysts in many reactions. Herein, the most recent advances, from recent papers and patents, in relation to the preparation of carbon-supported Pd or Ru nanoparticles systems as well as their application as catalysts in alcohol oxidation, cross-coupling or hydrogenation reactions, are reviewed.

  13. Dissolution Process of Palladium in Hydrochloric Acid: A Route via Alkali Metal Palladates (United States)

    Kasuya, Ryo; Miki, Takeshi; Morikawa, Hisashi; Tai, Yutaka


    To improve the safety of the Pd recovery processes that use toxic oxidizers, dissolution of Pd in hydrochloric acid with alkali metal palladates was investigated. Alkali metal palladates were prepared by calcining a mixture of Pd black and alkali metal (Li, Na, and K) carbonates in air. Almost the entire amount of Pd was converted into Li2PdO2 after calcination at 1073 K (800 °C) using Li2CO3. In contrast, PdO was obtained by calcination at 1073 K (800 °C) using Na and K carbonates. Our results indicated that Li2CO3 is the most active reagent among the examined alkali metal carbonates for the formation of palladates. In addition, dissolution of the resulting Li2PdO2 in HCl solutions was evaluated under various conditions. In particular, Li2PdO2 rapidly dissolved in diluted (0.1 M) HCl at ambient temperature. Solubility of Pd of Li2PdO2 was found to be 99 pct or larger after dissolution treatment at 353 K (80 °C) for 5 minutes; in contrast, PdO hardly dissolved in 0.1 M HCl. The dissolution mechanism of Li2PdO2 in HCl was also elucidated by analysis of crystal structures and particulate properties. Since our process is completely free from toxic oxidizers, the dissolution process via alkali metal palladates is much safer than currently employed methods.

  14. Study on the Reaction Mechanism for Carbon Dioxide Reforming of Methane over supported Nickel Catalyst

    Institute of Scientific and Technical Information of China (English)

    Ling QIAN; Zi Feng YAN


    The adsorption and dissociation of methane and carbon dioxide for reforming on nickelcatalyst were extensively investigated by TPSR and TPD experiments. It showed that thedecomposition of methane results in the formation of at least three kinds of surface carbon specieson supported nickel catalyst, while CO2 adsorbed on the catalyst weakly and only existed in onekind of adsorption state. Then the mechanism of interaction between the species dissociatedfrom CH4 and CO2 during reforming was proposed.

  15. Mechanism and Stereoselectivity in an Asymmetric N-Heterocyclic Carbene-Catalyzed Carbon-Carbon Bond Activation Reaction. (United States)

    Pareek, Monika; Sunoj, Raghavan B


    The mechanism and origin of stereoinduction in a chiral N-heterocyclic carbene (NHC) catalyzed C-C bond activation of cyclobutenone has been established using B3LYP-D3 density functional theory computations. The activation of cyclobutenone as an NHC-bound vinyl enolate and subsequent reaction with the electrophilic sulfonyl imine leads to the lactam product. The most preferred stereocontrolling transition state exhibits a number of noncovalent interactions rendering additional stabilization. The computed enantio- and diastereoselectivities are in good agreement with the previous experimental observations.

  16. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

    Directory of Open Access Journals (Sweden)

    Sandesh Y. Sawant


    Full Text Available Microbial fuel cells (MFCs are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR. Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored.

  17. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells (United States)

    Sawant, Sandesh Y.; Han, Thi Hiep; Cho, Moo Hwan


    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored. PMID:28029116

  18. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells. (United States)

    Sawant, Sandesh Y; Han, Thi Hiep; Cho, Moo Hwan


    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored.

  19. A Nodular Foreign Body Reaction in a Dialysis Patient Receiving Long-term Treatment With Lanthanum Carbonate. (United States)

    Valika, Aziz K; Jain, Dhanpat; Jaffe, Phillip E; Moeckel, Gilbert; Brewster, Ursula C


    A 63-year-old man with HIV (human immunodeficiency virus) infection and end-stage renal disease, treated with lanthanum carbonate phosphate binder for 4 years, presented with anemia and an upper gastrointestinal bleed. Upper endoscopy revealed a nodular hyperplastic epithelium, with an endoscopic ultrasound confirming hyperechoic material within the nodules. Light microscopy showed collections of histiocytes and multinucleated giant cells containing brown granular cytoplasmic material and extracellular crystalline material, a finding confirmed by electron microscopy. Similar pathologic findings associated with lanthanum exposure have been described recently. In our patient, lanthanum carbonate treatment was withdrawn and gastrointestinal bleeding has since ceased. The patient was exposed to a high amount of lanthanum over a long period, which may explain his adverse reaction. However, other contributing factors, such as competing medications or comorbid conditions, also may have increased his sensitivity to the drug.

  20. Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wu; Xu, Kang; Viswanathan, Vilayanur V.; Towne, Silas A.; Hardy, John S.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Wang, Deyu; Zhang, Jiguang


    The Li-O2 chemistry in nonaqueous carbonate electrolytes and the underneath reason of its limited reversibility was exhaustively investigated. The discharge products collected from the air cathode in a Li-O2 battery at different depth of discharge (DOD) were systematically analyzed with X-ray diffraction. It is revealed that, independent of the discharge depth, lithium alkylcarbonate (either lithium propylenedicarbonate - LPDC, or lithium ethylenedicarbonate - LEDC, with other related derivatives) and lithium carbonate (Li2CO3) are always the main products, obviously originated from the electrolyte solvents propylene carbonate (PC) and ethylene carbonate (EC). These lithium alkylcarbonates are obviously generated from the single-electron reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. On the other hand, neither lithium peroxide (Li2O2) nor lithium oxide (Li2O) is detected. More significantly, from in situ gas chromatography/mass spectroscopy it is found that Li2CO3 and Li2O cannot be oxidized even when charged up to 4.6 V vs. Li/Li+, while LPDC, LEDC and Li2O2 are readily able to, with CO2 and CO released with the re-oxidation of LPDC and LEDC. It is therefore concluded that the quasi-reversibility of Li-O2 chemistry observed hitherto in an organic carbonate-based electrolyte is actually reliant on the formation of lithium alkylcarbonates through the reductive decomposition of carbonate solvents during discharge process and the subsequent oxidation of these same alkylcarbonates during charge process. It is the poor oxidizability of these alkylcarbonate species that constitutes the obstruction to an ideal rechargeable Li-O2 battery.

  1. Dimethyl carbonate synthesis via transesterification of propylene carbonate with methanol by ceria-zinc catalysts: Role of catalyst support and reaction parameters

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Praveen; Srivastava, Vimal Chandra; Mishra, Indra Mani [Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand (India)


    Ceria and zinc oxide catalyst were impregnated onto various oxide supports, namely Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, individually by deposition-coprecipitation method. The synthesized catalysts (CZA, CZS and CZT having supports Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, respectively) were characterized by X-ray diffraction (XRD), NH{sub 3}- and CO{sub 2}-temperature programmed desorption (TPD) and N2 adsorption. These catalysts were used for synthesis of dimethyl carbonate (DMC) from methanol and propylene carbonate in a batch reactor. CZS was found to have larger average grain size as compared to CZA and CZT. Composite oxides (catalysts) were found to contain individual phases of ZnO, CeO{sub 2} and some spinel forms of Zn, Ce along with their supports. CZS having highest basicity and surface area showed better catalytic activity as compared to CZA and CZT. Effect of reaction temperature and methanol/PC molar ratio on DMC yield was studied and a reaction mechanism has been discussed. Maximum DMC yield of 77% was observed with CZS catalyst at 170 .deg. C with methanol/PC molar ratio of 10.

  2. Synthesis and Characterization of Graphene and Graphene Oxide Based Palladium Nanocomposites and Their Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Minjae [Kunsan National Univ., Gunsan (Korea, Republic of); Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B. [Chonbuk National Univ., Jeonju (Korea, Republic of)


    We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in H{sub 2} and O{sub 2} gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.

  3. Quantum Chemistry Study of Cycloaddition Pathways for the Reaction of o-Benzyne with Fullerenes and Carbon Nanotubes (United States)

    Jaffe, Richard; Han, Jie; Langhoff, Stephen R. (Technical Monitor)


    Functionalization of fullerenes via the [2+2] cycloaddition reaction with o-benzyne has been demonstrated in the laboratory. In contrast, [2+4) cycloaddition products are formed when benzyne reacts with planar polycyclic aromatic hydrocarbons. Using density functional theory (DFT) calculations with Becke's hybrid functional and small contracted gaussian basis sets, we are able to reproduce these product preferences. The objective of this work is to explore the functionalization of carbon nanotubes. We have studied o-benzyne cycloaddition products with a [14,0] single-walled nanotube. We find both the [2+2] and [2+4] adducts to be stable, with the latter product being somewhat favored.

  4. A prediction model for concrete carbonation based on coupled CO²-H²O-ions transfers and chemical reactions



    It is a recognized fact that steel corrosion reduces the serviceability and safety performance of reinforced concrete. Usually high alkaline conditions in concrete lead to the formation of a passive layer at the steel surface. However the natural diffusion of the atmospheric carbon dioxide (CO²) into the concrete induces a decrease of the pore water pH value after reactions with hydrates such as portlandite Ca(OH)² and calcium silicate hydrates C-S-H. Under low-pH conditions, the passive laye...

  5. Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Yi Cheng


    Full Text Available The water electrolysis for hydrogen production is constrained by the thermodynamically unfavorable oxygen evolution reaction (OER, which requires input of a large amount of energy to drive the reaction. One of the key challenges to increase the efficiency of the water electrolysis system is to develop highly effective and robust electrocatalysts for the OER. In the past 20–30 years, significant progresses have been made in the development of efficient electrocatalysts, including metal oxides, metal oxide-carbon nanotubes (CNTs hybrid and metal-free CNTs based materials for the OER. In this critical review, the overall progress of metal oxides catalysts and the role of CNTs in the development of OER catalyst are summarized, and the latest development of new metal free CNTs-based OER catalyst is discussed.

  6. Hydrogen evolution reaction at Ru-modified nickel-coated carbon fibre in 0.1 M NaOH

    Directory of Open Access Journals (Sweden)

    Pierożyński Bogusław


    Full Text Available The electrochemical activity towards hydrogen evolution reaction (HER was studied on commercially available (Toho-Tenax and Ru-modified nickel-coated carbon fibre (NiCCF materials. Quality and extent of Ru electrodeposition on NiCCF tows were examined by means of scanning electron microscopy (SEM. Kinetics of the hydrogen evolution reaction were investigated at room temperature, as well as over the temperature range: 20-50°C in 0.1 M NaOH solution for the cathodic overpotential range: -100 to -300 mV vs. RHE. Corresponding values of charge-transfer resistance, exchange current-density for the HER and other electrochemical parameters for the examined fibre tow composites were recorded.

  7. Sensitivity of chemical reaction networks: a structural approach. 1. Examples and the carbon metabolic network. (United States)

    Mochizuki, Atsushi; Fiedler, Bernold


    In biological cells, chemical reaction pathways lead to complex network systems like metabolic networks. One experimental approach to the dynamics of such systems examines their "sensitivity": each enzyme mediating a reaction in the system is increased/decreased or knocked out separately, and the responses in the concentrations of chemicals or their fluxes are observed. In this study, we present a mathematical method, named structural sensitivity analysis, to determine the sensitivity of reaction systems from information on the network alone. We investigate how the sensitivity responses of chemicals in a reaction network depend on the structure of the network, and on the position of the perturbed reaction in the network. We establish and prove some general rules which relate the sensitivity response to the structure of the underlying network. We describe a hierarchical pattern in the flux response which is governed by branchings in the network. We apply our method to several hypothetical and real life chemical reaction networks, including the metabolic network of the Escherichia coli TCA cycle.

  8. In Situ Evaluation of Water-Rock Reactions during Carbon Dioxide Injection in Basaltic and Metasedimentary Rocks (United States)

    Matter, J. M.; Assayag, N.; Goldberg, D.; Takahashi, T.


    Large differences between laboratory and field derived mineral reaction rates underscore the importance of evaluating mineral-fluid reactions under in situ conditions in a natural environment. This study investigates the extent of in situ water-rock reactions in basaltic and metasedimentary rocks (rich in Ca, Mg silicates) after the injection of CO2 enriched water, with the objective of providing information pertinent to permanent storage of anthropogenic CO2 in geologic reservoirs. CO2 injections were conducted using a single-well push-pull testing strategy. CO2 saturated water (pH 3.5) was injected into a hydraulically isolated and permeable aquifer in a 300-m experimental borehole. Water samples were retrieved after the CO2 injection. Mass transfer terms for Ca, Mg, Na, and Si were determined by using the measured ion concentrations. Using the mass balance, the weeks-long incubation time of the injected solution, and geometric estimates of the reactive surface area of the host rocks, in situ bulk rock dissolution rates of aquifer material were estimated. In addition, δ13C data coupled with total CO2 concentration were used as a tracer to quantitatively evaluate processes such as carbonate dissolution and precipitation, oxidation of organic matter and biological activity within the aquifer. Results show that the injected CO2 was neutralized within several days by two processes; mixing with aquifer water, and rock-water reactions. Calculated bulk rock dissolution rates decrease with increasing pH. The pH dependence of the dissolution rate for Ca is twice as large as for Mg, strongly favoring Ca release and possibly suggesting an additional source of Ca besides silicate minerals. Analyses of δ13C on water and rock samples confirm dissolution of calcium carbonates within the aquifer.

  9. Improving the electrocatalytic performance of carbon nanotubes for VO2+/VO2+ redox reaction by KOH activation (United States)

    Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing


    In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO2+/VO2+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO2+/VO2+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO2+/VO2+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO2+/VO2+ redox reaction for VRFB system.

  10. A DFT study on the mechanism of palladium-catalyzed divergent reactions of 1,6-enyne carbonates

    Indian Academy of Sciences (India)

    Xing Hui Zhang; Zhi Yuan Geng; Teng Niu; Ke Tai Wang


    The reaction mechanisms of palladium-catalyzed divergent reactions of 1,6-enyne carbonates have been investigated using DFT calculations at the B3LYP/6-31G(d,p) (LanL2DZ for Pd) level. Solvent effects on these reactions have been considered by the polarizable continuum model (PCM) for the solvent (DMF). The formation of vinylidenepyridines and vinylidenepyrrolidines were generated through 5-exo-dig cyclization or 6-endo-dig cyclization. Our calculation results suggested the following: (i) The first step of the whole cycle is the rate-determining step, which causes allenic palladium intermediate through two plausible pathways. This intermediate provides the corresponding products and releases the palladium catalyst by a subsequent hydrogen transfer and elimination process. (ii) For the catalyst CH3OPdH, the reaction could occur through two possible pathways, but 5-exo-dig cyclization is favoured over 6-endo-dig cyclization. However, when the hydrogen atom is substituted with a phenyl group, the energy barriers for 5-exo-dig cyclization or 6-endo-dig cyclization become relatively high, 18.0–28.5 kcal/mol. The computational results provide good explanation for the experimental observations.

  11. Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase. (United States)

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


    The carbonate radical anion CO3(•-) is a key intermediate in tropospheric anion chemistry. Despite its radical character, only a small number of reactions have been reported in the literature. Here we investigate the gas-phase reactions of CO3(•-) and CO3(•-)(H2O) with HCl under ultrahigh vacuum conditions. Bare CO3(•-) forms OHCl(•-) with a rate constant of 4.2 × 10(-12) cm(3) s(-1), which corresponds to an efficiency of only 0.4%. Hydration accelerates the reaction, and ligand exchange of H2O against HCl proceeds with a rate of 2.7 × 10(-10) cm(3) s(-1). Quantum chemical calculations reveal that OHCl(•-) is best described as an OH(•) hydrogen bonded to Cl(-), while the ligand exchange product is Cl(-)(HCO3(•)). Under tropospheric conditions, where CO3(•-)(H2O) is the dominant species, Cl(-)(HCO3(•)) is efficiently formed. These reactions must be included in models of tropospheric anion chemistry.

  12. A nitrogen-doped mesoporous carbon containing an embedded network of carbon nanotubes as a highly efficient catalyst for the oxygen reduction reaction. (United States)

    Li, Jin-Cheng; Zhao, Shi-Yong; Hou, Peng-Xiang; Fang, Ruo-Pian; Liu, Chang; Liang, Ji; Luan, Jian; Shan, Xu-Yi; Cheng, Hui-Ming


    A nitrogen-doped mesoporous carbon containing a network of carbon nanotubes (CNTs) was produced for use as a catalyst for the oxygen reduction reaction (ORR). SiO2 nanoparticles were decorated with clusters of Fe atoms to act as catalyst seeds for CNT growth, after which the material was impregnated with aniline. After polymerization of the aniline, the material was pyrolysed and the SiO2 was removed by acid treatment. The resulting carbon-based hybrid also contained some Fe from the CNT growth catalyst and was doped with N from the aniline. The Fe-N species act as active catalytic sites and the CNT network enables efficient electron transport in the material. Mesopores left by the removal of the SiO2 template provide short transport pathways and easy access to ions. As a result, the catalyst showed not only excellent ORR activity, with 59 mV more positive onset potential and 30 mV more positive half-wave potential than a Pt/C catalyst, but also much longer durability and stronger tolerance to methanol crossover than a Pt/C catalyst.

  13. Comparative study on the oxygen reduction reaction electrocatalytic activities of iron phthalocyanines supported on reduced graphene oxide, mesoporous carbon vesicle, and ordered mesoporous carbon (United States)

    Li, Mian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping


    Iron phthalocyanine (FePc) is combined with different carbon matrixes (reduced graphene oxide (RGO), mesoporous carbon vesicle (MCV), and ordered mesoporous carbon (OMC)) through non-covalent π-π interaction. The nitrogen adsorption-desorption isotherms display that their specific surface areas obey an order of OMC > MCV > RGO. Raman spectroscopy reveals that OMC contains the most surface active sites. Meanwhile, SEM images show that the FePc monomers are more evenly dispersed on OMC than on MCV or RGO. Electrochemical measurements also display that oxygen reduction reaction (ORR) is catalyzed more easily on the FePc/OMC than on the FePc, FePc/MCV, and FePc/RGO, undoubtedly testifying the importances of specific surface area and surface active sites of OMC matrix for uniformly dispersing FePc molecules and then improving the ORR performances. Particularly, experiment results reveal that the FePc/OMC catalyst displays an enhanced 4-electron pathway in ORR either in acid or in alkaline media. Meanwhile, the FePc/OMC also shows better durability and superior stability towards methanol crossover than the Pt/OMC catalyst in both acid and alkaline media, potentially making the FePc/OMC a non-precious metal catalyst for ORR in fuel cells.

  14. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin [UC


    We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

  15. Effects of reaction conditions on hydrogen production and carbon nanofiber properties generated by methane decomposition in a fixed bed reactor using a NiCuAl catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Suelves, I.; Pinilla, J.L.; Lazaro, M.J.; Moliner, R. [Instituto de Carboquimica CSIC, Miguel Luesma Castan, 4, 50015 Zaragoza (Spain); Palacios, J.M. [Instituto de Catalisis y Petroleoquimica, CSIC, Cantoblanco, Marie Curie 2, 28049 Madrid (Spain)


    In this paper, the results obtained in the catalytic decomposition of methane in a fixed bed reactor using a NiCuAl catalyst prepared by the fusion method are presented. The influences of reaction temperature and space velocity on hydrogen concentration in the outlet gases, as well as on the properties of the carbon produced, have been investigated. Reaction temperature and the space velocity both increase the reaction rate of methane decomposition, but also cause an increase in the rate of catalyst deactivation. Under the operating conditions used, the carbon product is mainly deposited as nanofibers with textural properties highly correlated with the degree of crystallinity. (author)

  16. Application of carbon dioxide towards the development of smart materials, green reaction schemes and metallic nanoparticle synthesis (United States)

    Mohammed, Fiaz S.

    Global carbon dioxide (CO2) emissions have steadily risen over the last 50 years, with 34 billion tons of CO2 released in 2009 alone. Its potential as a greenhouse gas has negatively affected of our lives and environment by the resulting ocean acidification and climate change. To mitigate atmospheric CO2, various strategies have been implemented for CO2 separation, capture, storage and use as a chemical feedstock. The use of CO2 in various chemical industries is attractive as its non-flammable, non-toxic, and relatively inert properties have made it an inherently safer alternative to traditional organic solvents, as well as, a greener carbon feedstock. Also, the accessible critical properties, appreciable critical density, high diffusivity and tunable thermophysical properties make liquid and supercritical CO2 an attractive solvent for industrial applications. In recent years, significant progress has been made in the field of tunable solvent media by employing the reversible reaction of CO2 with amines to produce carbamates. This class of compounds possesses ionic properties that are significantly different from their amines resulting in a non-ionic to ionic switching mechanism that provides for switchable solvent properties, reversible surfactants, low molecular weight organogelators and stimuli responsive materials. The focus of this dissertation is therefore the implementation of the reversible CO2—amine reaction for the formation of smart surfaces, greener amine protection mechanisms, and cationic metallic nanoparticle synthesis. Chapter 2 of this dissertation demonstrates the reversible reaction of CO2 with amine-containing self-assembled monolayers to yield "smart" surfaces that undergo a reversible change in structure, charge, and wettability upon reaction with CO2. The formation carbamate esters are also a widely implemented mechanism for amine protection during organic synthesis. However, traditional methods of protection incur increased solvent use and

  17. Effect of carbon on wettability and interface reaction between melt superalloy and ceramic material

    Directory of Open Access Journals (Sweden)

    Chen Xiaoyan


    Full Text Available Effect of C on wettability and interface reaction between a nickel based superalloy and ceramic material was investigated by using a sessile drop method. It was found that the content of C in the alloy is able to influence the wettability and interface reaction. Alloys with C content lower than 0.1wt.% are stable on ceramic material and no interface reaction generates at the alloy-ceramic interface. However, when C content is higher than 0.1wt.%, the interface reaction occurs and the wetting angle decreases quickly. The product of interface reaction is discontinuous and composed of 9Al2O3 ⋅Cr2O3. Such result indicates that Cr in the alloy is impossible to react with the ceramic material and form Cr2O3 without the assistance of C. It is suggested that C in the alloy deoxidizes SiO2 in the ceramic material and produces SiO and CO. SiO is unstable and it can release active O atom at the interface. Cr at the interface combines with free O atom and forms Cr2O3. Al2O3 in the ceramic material and Cr2O3 finally forms 9Al2O3 ⋅Cr2O3.

  18. Partial Oxidation of Butane to Syngas over Nickel SupportedCatalysts Modified by Alkali Metal Oxide and Rare-Earth Metal Oxide

    Institute of Scientific and Technical Information of China (English)


    The partial oxidation of butane (POB) to syngas over nickel supported catalysts was first investigated with a flow-reactor, TG and UVRRS. The NiO/g-Al2O3 is the most suitable for the POB among NiO/g-Al2O3, NiO/MgO and NiO/SiO2. And the reaction performance of the NiO/g-Al2O3 shows little difference from those of the nickel supported catalysts modified by alkali metal oxide and rare-earth metal oxide. However, modification with Li2O and La2O3 can suppress carbon-deposition of the NiO/g-Al2O3, which contains graphite-like species during the POB reaction.

  19. Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. (United States)

    Deng, Dehui; Yu, Liang; Chen, Xiaoqi; Wang, Guoxiong; Jin, Li; Pan, Xiulian; Deng, Jiao; Sun, Gongquan; Bao, Xinhe


    Chainmail for catalysts: a catalyst with iron nanoparticles confined inside pea-pod-like carbon nanotubes exhibits a high activity and remarkable stability as a cathode catalyst in polymer electrolyte membrane fuel cells (PEMFC), even in presence of SO(2). The approach offers a new route to electro- and heterogeneous catalysts for harsh conditions.

  20. Miniaturized reaction chamber for optimized laser-assisted carbon nanotube growth

    NARCIS (Netherlands)

    Burgt, Y. van de; Loon, W. van; Mandamparambil, R.; Bellouard, Y.


    The localized growth of carbon nanotube structures has potential in many applications such as interconnects, field emitters and sensors. Using a laser to locally heat the substrate offers a highly versatile process compatible with a broad range of substrates and devices. However, for laser-assisted

  1. Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)


    Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

  2. Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution. (United States)

    Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami


    Calcium carbonate (CaCO3) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO4·2H2O and CaSO4 transformed into calcite, a polymorph of CaCO3, while maintaining their macroscopic structure when immersed in 1mol/L Na2CO3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO4·2H2O and CaSO4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO4·2H2O and CaSO4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors.

  3. The Development and Application of Two-Chamber Reactors and Carbon Monoxide Precursors for Safe Carbonylation Reactions. (United States)

    Friis, Stig D; Lindhardt, Anders T; Skrydstrup, Troels


    Low molecular weight gases (e.g., carbon monoxide, hydrogen, and ethylene) represent vital building blocks for the construction of a wide array of organic molecules. Whereas experimental organic chemists routinely handle solid and liquid reagents, the same is not the case for gaseous reagents. Synthetic transformations employing such reagents are commonly conducted under pressure in autoclaves or under atmospheric pressure with a balloon setup, which necessitates either specialized equipment or potentially hazardous and nonrecommended installations. Other safety concerns associated with gaseous reagents may include their toxicity and flammability and, with certain gases, their inability to be detected by human senses. Despite these significant drawbacks, industrial processes apply gaseous building blocks regularly due to their low cost and ready availability but nevertheless under a strictly controlled manner. Carbon monoxide (CO) fits with all the parameters for being a gas of immense industrial importance but with severe handling restrictions due to its inherent toxicity and flammability. In academia, as well as research and development laboratories, CO is often avoided because of these safety issues, which is a limitation for the development of new carbonylation reactions. With our desire to address the handling of CO in a laboratory setting, we designed and developed a two-chamber reactor (COware) for the controlled delivery and utilization of stoichiometric amounts of CO for Pd-catalyzed carbonylation reactions. In addition to COware, two stable and solid CO-releasing molecules (COgen and SilaCOgen) were developed, both of which release CO upon activation by either Pd catalysis or fluoride addition, respectively. The unique combination of COware with either COgen or SilaCOgen provides a simple reactor setup enabling synthetic chemists to easily perform safe carbonylation chemistry without the need for directly handling the gaseous reagent. With this technology

  4. Hypercalcemic encephalopathy due to milk alkali syndrome and injection teriparatide

    Directory of Open Access Journals (Sweden)

    Sandeep Kharb


    Full Text Available An 82-year-old male, a known case of severe osteoporosis with vertebral fracture and prostatic carcinoma, was treated with gonadotropin releasing hormone analogue, calcium carbonate, cholecalciferol sachet and injection teriparatide. His diet consisted of milk and curd. He developed altered behavior and generalized weakness, and on investigation, hypercalcemia, hypokalemia, and metabolic alkalosis with low parathyroid hormone levels were detected. Injection teriparatide was stopped and he was managed with forced saline diuresis and injection zoledronic acid. He was diagnosed as a case of milk alkali syndrome in whom teriparatide and prolonged immobilization played a permissive role in the development of hypercalcemic encephalopathy.

  5. Chemical compatibility of structural materials in alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Natesan, K.; Rink, D.L.; Haglund, R. [Argonne National Lab., Chicago, IL (United States)] [and others


    The objectives of this task are to (a) evaluate the chemical compatibility of structural alloys such as V-5 wt.%Cr-5 wt.%Ti alloy and Type 316 stainless steel for application in liquid alkali metals such as lithium and sodium-78 wt.% potassium (NaK) at temperatures in the range that are of interest for International Thermonuclear Experimental Reactor (ITER); (b) evaluate the transfer of nonmetallic elements such as oxygen, nitrogen, carbon, and hydrogen between structural materials and liquid metals; and (c) evaluate the effects of such transfers on the mechanical and microstructural characteristics of the materials for long-term service in liquid-metal-environments.

  6. Sustainable Ways of Combining Reactions and Separations Using Ionic Liquids and Carbon Dioxide

    NARCIS (Netherlands)

    Kazemi, S.


    Traditional chemical processes show shortcomings caused by using volatile organic compounds as solvents during reactions and separations. Therefore, it is necessary to address this issue by moving toward more environmentally friendly processes. This is possible by using less toxic and hazardous solv

  7. Transition Metal Catalyzed Reactions for Forming Carbon–Oxygen and Carbon–Carbon Bonds

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte

    of hydrogen per formed mol of ester as assumed. Furthermore a disproportionation mechanism (Tishchenko) could be ruled out due to the fact that free aldehydes did not enter the catalytic cycle. Fast deuterium/hydrogen exchange in the reaction with benzyl alcohol points towards a ruthenium dihydride species...... eliminates a bromo radical and forms the product....

  8. Modular, Catalytic Enantioselective Construction of Quaternary Carbon Stereocenters by Sequential Cross-Coupling Reactions. (United States)

    Potter, Bowman; Edelstein, Emma K; Morken, James P


    The catalytic Suzuki-Miyaura cross-coupling with chiral γ,γ-disubstituted allylboronates in the presence of RuPhos ligand occurs with high regioselectivity and enantiospecificity, furnishing nonracemic compounds with quaternary centers. Mechanistic experiments suggest that the reaction occurs by transmetalation with allyl migration, followed by rapid reductive elimination.

  9. A Dramatic Classroom Demonstration of Limiting Reagent Using the Vinegar and Sodium Hydrogen Carbonate Reaction (United States)

    Artdej, Romklao; Thongpanchang, Tienthong


    This demonstration is designed to illustrate the concept of limiting reagent in a spectacular way. Via a series of experiments where the amount of vinegar is fixed and the amount of NaHCO[subscript 3] is gradually increased, the volume of CO[subscript 2] generated from the reaction varies corresponding to the amount of NaHCO[subscript 3] until it…

  10. Reaction dynamics of {sup 34-38}Mg projectile with carbon target using Glauber model

    Energy Technology Data Exchange (ETDEWEB)

    Shama, Mahesh K., E-mail: [School of Physics and Material Sciences, Thapar University Patiala-147004 (India); Department of Applied Sciences, Chandigarh Engineering College, Landran Mohali-140307 (India); Panda, R. N. [Department of Physics, ITER, Shiksha O Anusandhan University, Bhubaneswar-751030 (India); Sharma, Manoj K. [School of Physics and Material Sciences, Thapar University Patiala-147004 (India); Patra, S. K. [Institute of Physics, Sachivalaya marg Bhubneswar-751005 (India)


    We have studied nuclear reaction cross-sections for {sup 34-38}Mg isotopes as projectile with {sup 12}C target at projectile energy 240AMeV using Glauber model with the conjunction of densities from relativistic mean filed formalism. We found good agreement with the available experimental data. The halo status of {sup 37}Mg is also investigated.

  11. Reaction mechanisms of aqueous monoethanolamine with carbon dioxide: a combined quantum chemical and molecular dynamics study. (United States)

    Hwang, Gyeong S; Stowe, Haley M; Paek, Eunsu; Manogaran, Dhivya


    Aqueous monoethanolamine (MEA) has been extensively studied as a solvent for CO2 capture, yet the underlying reaction mechanisms are still not fully understood. Combined ab initio and classical molecular dynamics simulations were performed to revisit and identify key elementary reactions and intermediates in 25-30 wt% aqueous MEA with CO2, by explicitly taking into account the structural and dynamic effects. Using static quantum chemical calculations, we also analyzed in more detail the fundamental interactions involved in the MEA-CO2 reaction. We find that both the CO2 capture by MEA and solvent regeneration follow a zwitterion-mediated two-step mechanism; from the zwitterionic intermediate, the relative probability between deprotonation (carbamate formation) and CO2 removal (MEA regeneration) tends to be determined largely by the interaction between the zwitterion and neighboring H2O molecules. In addition, our calculations clearly demonstrate that proton transfer in the MEA-CO2-H2O solution primarily occurs through H-bonded water bridges, and thus the availability and arrangement of H2O molecules also directly impacts the protonation and/or deprotonation of MEA and its derivatives. This improved understanding should contribute to developing more comprehensive kinetic models for use in modeling and optimizing the CO2 capture process. Moreover, this work highlights the importance of a detailed atomic-level description of the solution structure and dynamics in order to better understand molecular mechanisms underlying the reaction of CO2 with aqueous amines.

  12. Pore-scale network modeling of microbially induced calcium carbonate precipitation: Insight into scale dependence of biogeochemical reaction rates (United States)

    Qin, Chao-Zhong; Hassanizadeh, S. Majid; Ebigbo, Anozie


    The engineering of microbially induced calcium carbonate precipitation (MICP) has attracted much attention in a number of applications, such as sealing of CO2 leakage pathways, soil stabilization, and subsurface remediation of radionuclides and toxic metals. The goal of this work is to gain insight into pore-scale processes of MICP and scale dependence of biogeochemical reaction rates. This will help us develop efficient field-scale MICP models. In this work, we have developed a comprehensive pore-network model for MICP, with geochemical speciation calculated by the open-source PHREEQC module. A numerical pseudo-3-D micromodel as the computational domain was generated by a novel pore-network generation method. We modeled a three-stage process in the engineering of MICP including the growth of biofilm, the injection of calcium-rich medium, and the precipitation of calcium carbonate. A number of test cases were conducted to illustrate how calcite precipitation was influenced by different operating conditions. In addition, we studied the possibility of reducing the computational effort by simplifying geochemical calculations. Finally, the effect of mass transfer limitation of possible carbonate ions in a pore element on calcite precipitation was explored.

  13. Effect of reaction environments on the reactivity of PCB (2-chlorobiphenyl) over activated carbon impregnated with palladized iron

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Hyeok [Department of Civil Engineering, University of Texas at Arlington, 416 Yates Drive, Arlington, TX 76019-0308 (United States); Al-Abed, Souhail R., E-mail: [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States)


    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-ClBP) in the RAC system. The results were discussed in close connection to the implementation issue of the RAC system for the remediation of contaminated sites with PCBs. Adsorption event of 2-ClBP onto RAC limited the overall performance under condition with a 2-ClBP/RAC mass ratio of less than 1.0 x 10{sup -4} above which dechlorination of 2-ClBP adsorbed to RAC was the reaction rate-determining step. Acidic and basic conditions were harmful to 2-ClBP adsorption and iron stability while neutral pH showed the highest adsorption-promoted dechlorination of 2-ClBP and negligible metal leaching. Coexisting natural organic matter (NOM) slightly inhibited 2-ClBP adsorption onto RAC due to the partial partitioning of 2-ClBP into NOM in the liquid phase while the 2-ClBP absorbed into NOM, which also tended to adsorb onto RAC, was less available for the dechlorination reaction. Common anions slowed down 2-ClBP adsorption but adsorbed 2-ClBP was almost simultaneously dechlorinated. Some exceptions included strong inhibitory effect of carbonate species on 2-ClBP adsorption and severe detrimental effect of sulfite on 2-ClBP dechlorination. Results on treatment of 2-ClBP spiked to actual sediment supernatants implied site-specific reactivity of RAC.

  14. Photosynthetic light reactions increase total lipid accumulation in carbon-supplemented batch cultures of Chlorella vulgaris. (United States)

    Woodworth, Benjamin D; Mead, Rebecca L; Nichols, Courtney N; Kolling, Derrick R J


    Microalgae are an attractive biofuel feedstock because of their high lipid to biomass ratios, lipid compositions that are suitable for biodiesel production, and the ability to grow on varied carbon sources. While algae can grow autotrophically, supplying an exogenous carbon source can increase growth rates and allow heterotrophic growth in the absence of light. Time course analyses of dextrose-supplemented Chlorella vulgaris batch cultures demonstrate that light availability directly influences growth rate, chlorophyll production, and total lipid accumulation. Parallel photomixotrophic and heterotrophic cultures grown to stationary phase reached the same amount of biomass, but total lipid content was higher for algae grown in the presence of light (an average of 1.90 mg/mL vs. 0.77 mg/mL over 5 days of stationary phase growth).

  15. In vivo MRI biocompatibility evaluation of functionalized carbon fibers in reaction with soft tissues

    Directory of Open Access Journals (Sweden)

    Prokić B.B.


    Full Text Available In modern medicine implants are very important and so is their design and choice of materials. Almost equally important is the choice of imaging technique used to in vivo monitor their fate and biocompatibility. The aim of this study was to evaluate the ability of magnetic resonance imaging (MRI in monitoring the biocompatibility of two newly designed carbon fibers. We have analyzed the interaction of surface functionalized carbon fibers (basic and acidic with muscle and subcutaneous tissues of rabbits. MRI techniques showed to be useful in longitudinal monitoring of the surrounding tissues, assessment of biocompatibility of new implants, and in the distinction of in vivo surgical edema from inflammation. Histopathology confirmed MRI results, thus showing that MRI has a great potential for in vivo studies of such materials. [Projekat Ministarstva nauke Republike Srbije, br. III 45006 and III 41005

  16. Fabrication of hollow carbon nanospheres encapsulating platinum nanoparticles using a photocatalytic reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Y.H.; Ikeda, S.; Harada, T.; Matsumura, M. [Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama, Toyonaka 560-8531 (Japan); Higashida, S. [Department of Industrial Chemistry, Osaka Prefectural College of Technology, 26-12 Saiwai, Neyagawa, Osaka 572-8572 (Japan); Sakata, T.; Mori, H. [Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, 7-1, Mihogaoka, Ibaraki 567-0047 (Japan)


    The fabrication of Pt nanoparticles encapsulated in hollow carbon nanospheres using TiO{sub 2} nanoparticles as both the photocatalyst and the inorganic mold is demonstrated. These spheres are found to have high surface area and ultrathin shells with well-developed microporosity, and thus can be used as catalysts. This new imprinting method can be used to synthesize any desired nanostructures using predesigned TiO{sub 2} photocatalysts. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  17. Carbon Nanotube/Boron Nitride Nanocomposite as a Significant Bifunctional Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions. (United States)

    Patil, Indrajit M; Lokanathan, Moorthi; Ganesan, Balakrishnan; Swami, Anita; Kakade, Bhalchandra


    It is an immense challenge to develop bifunctional electrocatalysts for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) in low temperature fuel cells and rechargeable metal-air batteries. Herein, a simple and cost-effective approach is developed to prepare novel materials based on carbon nanotubes (CNTs) and a hexagonal boron nitride (h-BN) nanocomposite (CNT/BN) through a one-step hydrothermal method. The structural analysis and morphology study confirms the formation of a homogeneous composite and merging of few exfoliated graphene layers of CNTs on the graphitic planes of h-BN, respectively. Moreover, the electrochemical study implies that CNT/BN nanocomposite shows a significantly higher ORR activity with a single step 4-electron transfer pathway and an improved onset potential of +0.86 V versus RHE and a current density of 5.78 mA cm(-2) in alkaline conditions. Interestingly, it exhibits appreciably better catalytic activity towards OER at low overpotential (η=0.38 V) under similar conditions. Moreover, this bifunctional catalyst shows substantially higher stability than a commercial Pt/C catalyst even after 5000 cycles. Additionally, this composite catalyst does not show any methanol oxidation reactions that nullify the issues due to fuel cross-over effects in direct methanol fuel cell applications.

  18. Assessment of the apparent activation energies for gas/solid reactions-carbonate decomposition

    Institute of Scientific and Technical Information of China (English)


    The guidelines for assessing the apparent activation energies of gas/solid reactions have been proposed based on the ex-perimental results from literatures. In CO2 free inlet gas flow, CaCO3 decomposition between 950 and 1250 K with thin sample layercould be controlled by the interfacial chemical reaction with apparent activation energy E = (215+10) kJ/mol and E = (200±10)kJ/mol at T = 813 to 1020 K, respectively. With relatively thick sample layer between 793 and 1273 K, the CaCO3 decompositioncould be controlled by one or more steps involving self-cooling, nucleation, intrinsic diffusion and heat transfer of gases, and E couldvary between 147 andl90 kJ/mol. In CO2 containing inlet gas flow (5%-100% of CO2), E was determined to be varied from 949 to2897 kJ/mol. For SrCO3 and BaCO3 decompositions controlled by the interfacial chemical reaction, E was (213+15) kJ/mol (1000-1350 K) and (305+15) kJ/mol (1260-1400 K), respectively.

  19. Nanosized alkali-metal-doped ethoxotitanate clusters. (United States)

    Chen, Yang; Trzop, Elzbieta; Makal, Anna; Sokolow, Jesse D; Coppens, Philip


    The synthesis and crystallographic characterization of alkali-metal-doped ethoxotitanate clusters with 28 and 29 Ti atoms as well as a new dopant-free Ti28 cluster are presented. The light-metal-doped polyoxotitanate clusters in which the alkali-metal atom is the critical structure-determining component are the largest synthesized so far. Calculations show that doping with light alkali atoms narrows the band gap compared with the nondoped crystals but does not introduce additional energy levels within the band gap.

  20. Thermophysical properties and reaction kinetics of γ-irradiated poly allyl diglycol carbonates nuclear track detector (United States)

    Elmaghraby, Elsayed K.; Seddik, Usama


    Kinetic thermogravimetric technique was used to study the effect of gamma irradiation on the poly allyl diglycol carbonates (PADC) within the dose range from 50 to ? Gy. The approach of Coats-Redfern was used to analyze the data. Results showed that low doses around 50 Gy make the polymer slightly more resistive to heat treatment. Higher radiation doses cause severe effects in the samples accompanied by the formation of lower molecular mass species and consequent crosslinking. Results support the domination of re-polymerization and crosslinking for the γ radiation interaction PADC at dose below about ? Gy, while the situation is inverted above ? Gy in which chain secession dominates.

  1. Carbon dioxide activation and reaction induced by electron transfer at an oxide-metal interface. (United States)

    Calaza, Florencia; Stiehler, Christian; Fujimori, Yuichi; Sterrer, Martin; Beeg, Sebastian; Ruiz-Oses, Miguel; Nilius, Niklas; Heyde, Markus; Parviainen, Teemu; Honkala, Karoliina; Häkkinen, Hannu; Freund, Hans-Joachim


    A model system has been created to shuttle electrons through a metal-insulator-metal (MIM) structure to induce the formation of a CO2 anion radical from adsorbed gas-phase carbon dioxide that subsequently reacts to form an oxalate species. The process is completely reversible, and thus allows the elementary steps involved to be studied at the atomic level. The oxalate species at the MIM interface have been identified locally by scanning tunneling microscopy, chemically by IR spectroscopy, and their formation verified by density functional calculations.

  2. A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions (United States)

    Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi


    A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique

  3. Metallic WO2-Carbon Mesoporous Nanowires as Highly Efficient Electrocatalysts for Hydrogen Evolution Reaction. (United States)

    Wu, Rui; Zhang, Jingfang; Shi, Yanmei; Liu, Dali; Zhang, Bin


    The development of electrocatalysts to generate hydrogen, with good activity and stability, is a great challenge in the fields of chemistry and energy. Here we demonstrate a "hitting three birds with one stone" method to synthesize less toxic metallic WO2-carbon mesoporous nanowires with high concentration of oxygen vacancies (OVs) via calcination of inorganic/organic WO3-ethylenediamine hybrid precursors. The products exhibit excellent performance for H2 generation: the onset overpotential is only 35 mV, the required overpotentials for 10 and 20 mA/cm(2) are 58 and 78 mV, the Tafel slope is 46 mV/decade, the exchange current density is 0.64 mA/cm(2), and the stability is over 10 h. Further studies, in combination with density functional theory, demonstrate that the unusual electronic structure and the large amount of active sites, generated by the high concentration of OVs, as well as the closely attached carbon materials, were key factors for excellent performance. Our results experimentally and theoretically establish metallic transition metal oxides (TMOs) as intriguing novel electrocatalysts for H2 generation. Such TMOs with OVs might be promising candidates for other energy storage and conversion applications.

  4. Dissolved Organic Carbon Determination Using FIA and Photo-Fenton Reaction

    Directory of Open Access Journals (Sweden)

    Kondo Márcia M.


    Full Text Available The FIA-photo-Fenton system is based on the flow oxidation of the organic matter. A small amount of the sample containing H2O2 is injected into the acidic flow solution of Fe2+, which passes through a tubular PTFE reactor irradiated with UV light. The generated CO2 is quantified by a conductometric detector and is directly proportional to the dissolved organic carbon concentration in the sample. The optimization studies were performed using EDTA solutions. The average recovery of organic carbon was 83% with a relative standard deviation of 3.7% using a 1:5 molar ratio of Fe2+:H2O2, pH 2.0, 100 muL of sample injection and a liquid flow of 1 mL min-1. After optimization, the DOC concentration was quantified using 13 different organic compounds, where the average recovery was 90%. The rate of the analysis was in average 50 samples hour-1.

  5. CO/sub 2/DBr precursor geometry limited reaction of deuterium with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Buelow, S.; Radhakrishnan, G.; Wittig, C.


    The authors report nascent OD(X/sup 2/II) rotational, vibrational, spin-orbit, and ..lambda..-doublet excitations from reactions of deuterium atoms with CO/sub 2/. D atoms are produced by the 193-nm photolysis of DBr (h nu - D/sub 0/ = 244 kJ mol/sup -1/) (i) within a weakly bonded CO/sub 2/DBr complex, and (ii) under 300 K single-collision bulk conditions. The differences between the resulting OD distributions are modest, and the present results are similar to those of the analogous H + CO/sub 2/ system.

  6. Understanding kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical. (United States)

    Bietti, Massimo; Martella, Roberto; Salamone, Michela


    A kinetic study of the hydrogen abstraction reactions from tetrahydrofuran (THF) and cyclohexane (CHX) by the cumyloxyl radical was carried out in different solvents. With THF, a 4.5-fold decrease in rate constant (k(H)) was observed on going from isooctane to 2,2,2-trifluoroethanol. An opposite behavior was observed with CHX, where k(H) increased by a factor 4 on going from isooctane to 2,2,2-trifluoroethanol. The important role of substrate structure and of the solvent hydrogen bond donor ability is discussed.

  7. Studies of One-Nucleon Transfer Reactions on Boron -11 and CARBON-12. (United States)

    Foot, Penelope Bernadette

    This thesis describes a study of the ^{11}B(d,n)^{12 }C and ^{12}C(t, alpha)^{11} B reactions. The Indiana University Cyclotron Facility produced the 79 MeV deuterons for the ^{11} B(d,n)^{12}C experiment. Time of flight measurements were performed to obtain neutron energy spectra. The energy resolution was typically 300 keV (~{1over 2} nsec). Cross sections were extracted for five well-resolved bound states in ^{12}C at 0.00, 4.44, 9.64, 12.71 and 15.11 MeV. The experimental cross sections were compared with the results of theoretical predictions. The effect of including, in these calculations, the breakup of the deuteron into low energy relative S states during the course of the reaction was investigated. Spectroscopic factors were then determined for the above five states in ^{12}C and compared with theoretical values. A subsequent experiment was performed at the same energy with vector polarized deuterons in order to study the effects of deuteron breakup on the corresponding analysing powers. This was the first time that analysing powers had been measured for this reaction. The effects on the cross section and analysing power calculations of exact finite range and the D state of the deuteron were investigated using the Reid soft-core potential for the proton-neutron interaction. The possible role of a two step process in the population of the 2 ^{+} state at 4.44 MeV in ^{12}C was examined. The effects on the analysing power for this state, of contributions from the 2p-1f shell in the 4.44 MeV wavefunction, were also discussed. Differential cross sections for the ^ {12}C(t,alpha) ^{11}B reaction, using 33 MeV tritons from the Daresbury Nuclear Structure Facility, were extracted for transitions to the 0.00, 2.125, 4.445, 5.021, 6.743, 7.286, 7.978 and 8.559 MeV states in ^{11 }B. The results of CRC calculations were compared with DWBA and CCBA calculation for the single step and two step transitions respectively. The spin of the 8.559 MeV state in ^{11}B, which

  8. Synergistic capture mechanisms for alkali and sulfur species from combustion. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Peterson, T.W.; Shadman, F.; Wendt, J.O.L.; Mwabe, P.O.


    Experimental work was carried out on a 17 kW, 600 cm long, gas laboratory combustor, to investigate the post flame reactive capture of alkali species by kaolinite. Emphasis was on alkali/sorbent interactions occurring in flue gas at temperatures above the alkali dewpoint and on the formation of water insoluble reaction products. Time-temperature studies were carried out by injecting kaolinite at different axial points along the combustor. The effect of chlorine and sulfur on alkali capture was investigated by doping the flame with SO{sub 2} and Cl{sub 2} gases to simulate coal flame environments. Particle time and temperature history was kept as close as possible to that which would ordinarily be found in a practical boiler. Experiments designed to extract apparent initial reaction rates were carried using a narrow range, 1-2 {mu}m modal size sorbent, while, a coarse, multi size sorbent was used to investigate the governing transport mechanisms. The capture reaction has been proposed to be between alkali hydroxide and activated kaolinite, and remains so in the presence of sulfur and chlorine. The presence of sulfur reduces sodium capture by under 10% at 1300{degree}C. Larger reductions at lower temperatures are attributed to the elevated dewpoint of sodium ({approximately}850{degree}C) with subsequent reduction in sorbent residence time in the alkali gas phase domain. Chlorine reduces sodium capture by 30% across the temperature range covered by the present experiments. This result has been linked to thermodynamic equilibria between sodium hydroxide, sodium chloride and water.

  9. Relaxation of quadrupole orientation in an optically pumped alkali vapour

    Energy Technology Data Exchange (ETDEWEB)

    Bernabeu, E.; Tornos, J.


    The relaxation of quadrupole orientation (alignment) in an optically pumped alkali vapour is theoretically studied by taking into account the relaxation processes by alkali-buffer gas, alkali-alkali with spin exchange and alkali-cell wall (diffusion process) collisions. The relaxation transients of the quadrupole orientation are obtained by introducing a first-order weak-pumping approximation (intermediate pumping) less restrictive than the usually considered (zeroth order) one.

  10. Milk Alkali and Hydrochlorothiazide: A Case Report

    Directory of Open Access Journals (Sweden)

    Babar Parvez


    Full Text Available Hypercalcemia is a relatively common clinical problem in both outpatient and inpatient settings. Primary pathophysiology is the entry of calcium that exceeds its excretion into urine or deposition in bone into circulation. Among a wide array of causes of hypercalcemia, hyperparathyroidism and malignancy are the most common, accounting for greater than 90 percent of cases. Concordantly, there has been a resurgence of milk-alkali syndrome associated with the ingestion of large amounts of calcium and absorbable alkali, making it the third leading cause of hypercalcemia (Beall and Scofield, 1995 and Picolos et al., 2005. This paper centers on a case of over-the-counter calcium and alkali ingestion for acid reflux leading to milk alkali with concordant use of thiazide diuretic for hypertension.

  11. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed. (United States)

    Gaikwad, Vaibhav; Kennedy, Eric; Mackie, John; Holdsworth, Clovia; Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael; Dlugogorski, Bogdan


    In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  12. Coprecipitation of {sup 14}C and Sr with carbonate precipitates: The importance of reaction kinetics and recrystallization pathways

    Energy Technology Data Exchange (ETDEWEB)

    Hodkin, David J. [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom); Stewart, Douglas I. [School of Civil Engineering, University of Leeds (United Kingdom); Graham, James T. [National Nuclear Laboratory, Sellafield, Cumbria (United Kingdom); Burke, Ian T., E-mail: [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom)


    This study investigated the simultaneous removal of Sr{sup 2+} and {sup 14}CO{sub 3}{sup 2−} from pH > 12 Ca(OH){sub 2} solution by the precipitation of calcium carbonate. Initial Ca{sup 2+}:CO{sub 3}{sup 2−} ratios ranged from 10:1 to 10:100 (mM:mM). Maximum removal of {sup 14}C and Sr{sup 2+} both occurred in the system containing 10 mM Ca{sup 2+} and 1 mM CO{sub 3}{sup 2−} (99.7% and 98.6% removal respectively). A kinetic model is provided that describes {sup 14}C and Sr removal in terms of mineral dissolution and precipitation reactions. The removal of {sup 14}C was achieved during the depletion of the initial TIC in solution, and was subsequently significantly affected by recrystallization of the calcite precipitate from an elongate to isotropic morphology. This liberated > 46% of the {sup 14}C back to solution. Sr{sup 2+} removal occurred as Ca{sup 2+} became depleted in solution and was not significantly affected by the recrystallization process. The proposed reaction could form the basis for low cost remediation scheme for {sup 90}Sr and {sup 14}C in radioactively contaminated waters (<$0.25 reagent cost per m{sup 3} treated). - Highlights: • 99.7% of {sup 14}C and 98.6% of Sr removed from aqueous solution by CaCO{sub 3} precipitation. • Remobilization of {sup 14}C observed during calcium carbonate recrystallization. • Sr displayed variable distribution coefficient (possibly affected by Ca:Sr ratio). • Reagent cost of $0.22/m{sup 3} of treated groundwater.

  13. Electrochemical Deposition of Platinum and Palladium on Gold Nanoparticles Loaded Carbon Nanotube Support for Oxidation Reactions in Fuel Cell

    Directory of Open Access Journals (Sweden)

    Surin Saipanya


    Full Text Available Pt and Pd sequentially electrodeposited Au nanoparticles loaded carbon nanotube (Au-CNT was prepared for the electrocatalytic study of methanol, ethanol, and formic acid oxidations. All electrochemical measurements were carried out in a three-electrode cell. A platinum wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. Suspension of the Au-CNT, phosphate buffer, isopropanol, and Nafion was mixed and dropped on glassy carbon as a working electrode. By sequential deposition method, PdPtPt/Au-CNT, PtPdPd/Au-CNT, and PtPdPt/Au-CNT catalysts were prepared. Cyclic voltammograms (CVs of those catalysts in 1 M H2SO4 solution showed hydrogen adsorption and hydrogen desorption reactions. CV responses for those three catalysts in methanol, ethanol, and formic acid electrooxidations studied in 2 M CH3OH, CH3CH2OH, and HCOOH in 1 M H2SO4 show characteristic oxidation peaks. The oxidation peaks at anodic scan contribute to those organic substance oxidations while the peaks at cathodic scan are related with the reoxidation of the adsorbed carbonaceous species. Comparing all those three catalysts, it can be found that the PdPtPt/Au-CNT catalyst is good at methanol oxidation; the PtPdPt/Au-CNT effectively enhances ethanol oxidation while the PtPdPd/Au-CNT exceptionally catalyzes formic acid oxidation. Therefore, a different stoichiometry affects the electrochemical active surface area of the catalysts to achieve the catalytic oxidation reactions.

  14. Effects of doping in 25-atom bimetallic nanocluster catalysts for carbon–carbon coupling reaction of iodoanisole and phenylacetylene

    Directory of Open Access Journals (Sweden)

    Zhimin Li


    Full Text Available We here report the catalytic effects of foreign atoms (Cu, Ag, and Pt doped into well-defined 25-gold-atom nanoclusters. Using the carbon-carbon coupling reaction of p-iodoanisole and phenylacetylene as a model reaction, the gold-based bimetallic MxAu25−x(SR18 (–SR=–SCH2CH2Ph nanoclusters (supported on titania were found to exhibit distinct effects on the conversion of p-iodoanisole as well as the selectivity for the Sonogashira cross-coupling product, 1-methoxy-4-(2-phenylethynylbenzene. Compared to Au25(SR18, the centrally doped Pt1Au24(SR18 causes a drop in catalytic activity but with the selectivity retained, while the AgxAu25−x(SR18 nanoclusters gave an overall performance comparable to Au25(SR18. Interestingly, CuxAu25−x(SR18 nanoclusters prefer the Ullmann homo-coupling pathway and give rise to product 4,4′-dimethoxy-1,1′-biphenyl, which is in opposite to the other three nanocluster catalysts. Our overall conclusion is that the conversion of p-iodoanisole is largely affected by the electronic effect in the bimetallic nanoclusters’ 13-atom core (i.e., Pt1Au12, CuxAu13−x, and Au13, with the exception of Ag doping, and that the selectivity is primarily determined by the type of atoms on the MxAu12−x shell (M=Ag, Cu, and Au in the nanocluster catalysts.

  15. Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism? (United States)

    Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel


    Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems

  16. Economic assessment of biodiesel production: Comparison of alkali and biocatalyst processes

    Energy Technology Data Exchange (ETDEWEB)

    Jegannathan, Kenthorai Raman [Department of Biotechnology, School of Biotechnology and Health sciences, Karunya University, Coimbatore, 641114 (India); Eng-Seng, Chan; Ravindra, Pogaku [Centre of Materials and Minerals, School of Engineering and Information Technology, University Malaysia Sabah, 88999 Kotakinabalu, Sabah (Malaysia)


    This study deals with the economic assessment of biodiesel production using three catalytic processes (1) alkali (2) soluble enzyme and (3) immobilized enzyme. All the processes were considered to be operated at batch mode with a production capacity of 10{sup 3} tonne. Biodiesel production cost using alkali catalyst process was found to be lowest ($ 1166.67/tonne) compared to soluble lipase catalyst ($ 7821.37/tonne) and immobilized lipase catalyst ($ 2414.63/tonne) process. The higher production cost was due to the higher cost of the enzyme and the higher reaction time of enzymatic process. However, reuse of immobilized catalyst decreased the production cost drastically unlike soluble enzyme catalyst. (author)

  17. An exploratory study of alkali sulfate aerosol formation during biomass combustion

    DEFF Research Database (Denmark)

    Løj, Lusi Hindiyarti; Frandsen, Flemming; Livbjerg, Hans;


    It is still in discussion to what extent alkali sulfate aerosols in biomass combustion are formed in the gas phase by a homogeneous mechanism or involve heterogeneous or catalyzed reactions. The present study investigates sulfate aerosol formation based on calculations with a detailed gas phase...... mechanism. The modeling predictions are compared to data from laboratory experiments and entrained flow reactor experiments available in the literature. The analysis support that alkali sulfate aerosols are formed from homogeneous nucleation following a series of steps occurring in the gas phase. The rate...

  18. Oxidation of the Boltysh deposit shale with atmosperic oxygen in a water-alkali medium

    Energy Technology Data Exchange (ETDEWEB)

    Proskuryakov, V.A.; Soloveichik, Z.V.; Yakovlev, V.I.


    Conditions for obtaining organic acids from Boltysh oil shale containing 43.12 percent organic matter were studied by oxidizing the shale with air in a water-alkali medium at different temperatures, oxidation times, and alkali consumptions. Maximum yield of 42.6 percent of high molecular acids was obtained at 175/sup 0/C; the yield of dibasic acids increased to 22 percent with increasing temperature. The degree of oxidation of shale kerogen increased from 55.6 to 79.6 percent with increase in oxidation time from 1 to 5 hours, the reaction proceeding stepwise from shale kerogen to high-molecular acids to dibasic acids.

  19. Composite of TiN nanoparticles and few-walled carbon nanotubes and its application to the electrocatalytic oxygen reduction reaction

    KAUST Repository

    Isogai, Shunsuke


    Nanoparticles meet nanotubes! Direct synthesis of TiN nanoparticles in a three-dimensional network of few-walled carbon nanotubes (FWCNTs) was achieved by using mesoporous graphitic carbon nitride (C 3N 4) as both a hard template and a nitrogen source. The TiN/FWCNT composite showed high performance for the oxygen reduction reaction in acidic media. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Recovery of kraft black liquor using the titanate process:kinetics of the direct causticization reaction between sodium tri-titanate and sodium carbonate


    Nohlgren, Ingrid


    The solid state reaction between sodium tri-titanate and sodium carbonate, forming mainly sodium penta-titanate, was investigated. Experiments were carried out in a micro-differential reactor made of quartz glass at various temperatures between 800°C and 880°C and in a pilot fluidized bed reactor operated in a semi-batch mode. In the micro-differential reactor, basic kinetic data was obtained by measuring the release of carbon dioxide during the reaction. Different kinetic models were conside...

  1. Carbon Supported Engineering NiCo2O4 Hybrid Nanofibers with Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Diab Hassan


    Full Text Available The design of cheap and efficient oxygen reduction reaction (ORR electrocatalysts is of a significant importance in sustainable and renewable energy technologies. Therefore, ORR catalysts with superb electrocatalytic activity and durability are becoming a necessity but still remain challenging. Herein, we report C/NiCo2O4 nanocomposite fibers fabricated by a straightforward electrospinning technique followed by a simple sintering process as a promising ORR electrocatalyst in alkaline condition. The mixed-valence oxide can offer numerous accessible active sites. In addition, the as-obtained C/NiCo2O4 hybrid reveals significantly remarkable electrocatalytic performance with a highly positive onset potential of 0.65 V, which is only 50 mV lower than that of commercially available Pt/C catalysts. The analyses indicate that C/NiCo2O4 catalyst can catalyze O2-molecules via direct four electron pathway in a similar behavior as commercial Pt/C catalysts dose. Compared to single NiCo2O4 and carbon free NiCo2O4, the C/NiCo2O4 hybrid displays higher ORR current and more positive half-wave potential. The incorporated carbon matrices are beneficial for fast electron transfer and can significantly impose an outstanding contribution to the electrocatalytic activity. Results indicate that the synthetic strategy hold a potential as efficient route to fabricate highly active nanostructures for practical use in energy technologies.

  2. Functional Species Encapsulated in Nitrogen-Doped Porous Carbon as a Highly Efficient Catalyst for the Oxygen Reduction Reaction. (United States)

    Song, Li; Wang, Tao; Ma, Yiou; Xue, Hairong; Guo, Hu; Fan, Xiaoli; Xia, Wei; Gong, Hao; He, Jianping


    The scarcity, high cost, and poor stability of precious metal-based electrocatalysts have stimulated the development of novel non-precious metal catalysts for the oxygen reduction reaction (ORR) for use in fuel cells and metal-air batteries. Here, we fabricated in situ a hybrid material (Co-W-C/N) with functional species (tungsten carbide and cobalt nanoparticles) encapsulated in an N-doped porous carbon framework, through a facile multi-constituent co-assembly method combined with subsequent annealing treatment. The unique structure favors the anchoring active nanoparticles and facilitates mass transfer steps. The homogenously distributed carbide nanoparticles and adjacent Co-N-C sites lead to the electrocatalytic synergism for the ORR. The existence of Co and W can promote the graphitization of the carbon matrix. Benefiting from its structural and material superiority, the Co-W-C/N electrocatalyst exhibits excellent electrocatalytic activity (with a half-wave potential of 0.774 V vs. reversible hydrogen electrode (RHE)), high stability (96.3 % of the initial current remaining after 9000 s of continuous operation), and good immunity against methanol in alkaline media.

  3. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction (United States)

    Yuan, Xianxia; Hu, Xin-Xin; Ding, Xin-Long; Kong, Hai-Chuan; Sha, Hao-Dong; Lin, He; Wen, Wen; Shen, Guangxia; Guo, Zhi; Ma, Zi-Feng; Yang, Yong


    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too.

  4. Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction (United States)

    Zhang, Jie; Chen, Jinwei; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin


    This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe3C and Co3C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe3C, and Co3C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.

  5. Effect of SiO2 on the Preparation and Properties of Pure Carbon Reaction Bonded Silicon Carbide Ceramics

    Institute of Scientific and Technical Information of China (English)

    WU Qi-de; GUO Bing-jian; YAN Yong-gao; ZHAO Xiu-jian; HONG Xiao-lin


    Effect of SiO2 content and sintering process on the composition and properties of Pure CarbonReaction Bonded Silicon Carbide (PCRBSC) ceramics prepared with C - SiO2 green body by infiltrating siliconwas presented. The infiltrating mechanism of C - SiO2 preform was also explored. The experimental results indicatethat the shaping pressure increases with the addition of SiO2 to the preform, and the pore size of the body turnedfiner and distributed in a narrower range, which is beneficial to decreasing the residual silicon content in the sin-tered materials and to avoiding shock off, thus increasing the conversion rate of SiC. SiO2 was deoxidized by car-bon at a high temperature and the gaseous SiO and CO produced are the main reason to the crack of the body atan elevated temperature. If the green body is deposited at 1800℃ in vacuum before infiltration crack will not beproduced in the preform and fully dense RBSC can be obtained. The ultimate material has the following properties:a density of3.05-3.12g/cm3 ,a strength of 580±32MPa and a hardness of (HRA)91-92.3.

  6. Plasma assisted measurements of alkali metal concentrations in pressurised combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Hernberg, R.; Haeyrinen, V. [Tampere Univ. of Technology (Finland)


    In this project the continuous alkali measurement method plasma excited alkali resonance line spectroscopy (PEARLS) was developed, tested and demonstrated in pressurised combustion facilities. The PEARLS method has been developed at Tampere University of Technology (TUT). During 1994-1996 the PEARLS method was developed from the laboratory level to an industrial prototype. The alkali measuring instrument has been tested and used for regular measurements in four different pressurised combustion installations ranging up to industrial pilot scale. The installations are: (1) a pressurised entrained flow reactor (PEFR) at VTT Energy in Jyvaeskylae, Finland (2) a pressurised fluidised bed combustion facility, called FRED, at DMT in Essen, Germany. (3) a 10 MW pressurised circulating fluidised bed combustion pilot plant at Foster Wheeler Energia Oy in Karhula, Finland (4) PFBC Research Facility at ABB Carbon in Finspaang, Sweden

  7. Remote Sensing of CO2 Absorption by Saline-Alkali Soils: Potentials and Constraints

    Directory of Open Access Journals (Sweden)

    Wenfeng Wang


    Full Text Available CO2 absorption by saline-alkali soils was recently demonstrated in the measurements of soil respiration fluxes in arid and semiarid ecosystems and hypothetically contributed to the long-thought “missing carbon sink.” This paper is aimed to develop the preliminary theory and methodology for the quantitative analysis of CO2 absorption by saline-alkali soils on regional and global scales. Both the technological progress of multispectral remote sensing over the past decades and the conjectures of mechanisms and controls of CO2 absorption by saline-alkali soils are advantageous for remote sensing of such absorption. At the end of this paper, the scheme for remote sensing is presented and some unresolved issues related to the scheme are also proposed for further investigations.

  8. A comprehensive theoretical study on the coupling reaction mechanism of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl. (United States)

    Guo, Cai-Hong; Wu, Hai-Shun; Zhang, Xian-Ming; Song, Jiang-Yu; Zhang, Xiang


    The mechanistic details of the coupling reaction of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl to yield cyclic carbonate were elucidated by density functional theory (DFT) calculations at the B3LYP/6-311G** level. Our results reveal that the overall reaction is stepwise and considered to include two processes. In process 1, CO(2) insertion into the Cu(I)-C bond of copper(I) cyanomethyl affords activated carbon dioxide carriers. In process 2, O-coordination of propylene oxide molecule to the electrophilic copper center of carriers occurs. Herein, three possible pathways were investigated, and the calculated reaction free energy profiles were compared. It was found that carrier 8 reacting with propylene oxide is more favored than the other two carriers (6 and 7) both kinetically and thermodynamically. Several factors, such as the composition of catalyst, the coordinate environment of copper, and the symmetry of frontier molecular orbitals, affected the reaction mechanisms, and the outcomes were identified. The overall reaction is exothermic. In addition, natural bond orbital (NBO) analysis has been performed to study the effects of charge transfer and understand the nature of different interactions between atoms and groups. The present theoretical study explains satisfactorily the early reported experimental observations well and provides a clear profile for the cycloaddition of carbon dioxide with propylene oxide promoted by NCCH(2)Cu.

  9. Structure of carbon-supported Pt-Ru nanoparticles and their electrocatalytic behavior for hydrogen oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Velazquez, Amado; Centellas, Francesc; Garrido, Jose Antonio; Arias, Conchita; Rodriguez, Rosa Maria; Brillas, Enric; Cabot, Pere-Lluis [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)


    The electrochemical activity towards hydrogen oxidation reaction (HOR) of a high performance carbon-supported Pt-Ru electrocatalyst (HP 20 wt.% 1:1 Pt-Ru alloy on Vulcan XC-72 carbon black) has been studied using the thin-film rotating disk electrode (RDE) technique. The physical properties of the Pt-Ru nanoparticles in the electrocatalyst were previously determined by transmission electron microscopy (TEM), high resolution TEM, fast Fourier transform (FFT), electron diffraction and X-ray diffraction (XRD). The corresponding compositional and size-shape analyses indicated that nanoparticles generally presented a 3D cubo-octahedral morphology with about 26 at.% Ru in the lattice positions of the face-centred cubic structure of Pt. The kinetics for HOR was studied in a hydrogen-saturated 0.5 M H{sub 2}SO{sub 4} solution using thin-film electrodes prepared by depositing an ink of the electrocatalyst with different Nafion contents in a one-step process on a glassy carbon electrode. A maximum electrochemically active surface area (ECSA) of 119 m{sup 2} g Pt{sup -1} was found for an optimum Nafion composition of the film of about 35 wt.%. The kinetic current density in the absence of mass transfer effects was 21 mA cm{sup -2}. A Tafel slope of 26 mV dec{sup -1}, independent of the rotation rate and Nafion content, was always obtained, evidencing that HOR behaves reversibly. The exchange current density referred to the ECSA of the Pt-Ru nanoparticles was 0.17 mA cm{sup -2}, a similar value to that previously found for analogous inks containing pure Pt nanoparticles. (author)

  10. Metal-Support Interactions of Platinum Nanoparticles Decorated N-Doped Carbon Nanofibers for the Oxygen Reduction Reaction. (United States)

    Melke, Julia; Peter, Benedikt; Habereder, Anja; Ziegler, Juergen; Fasel, Claudia; Nefedov, Alexei; Sezen, Hikmet; Wöll, Christof; Ehrenberg, Helmut; Roth, Christina


    N-doped carbon materials are discussed as catalyst supports for the electrochemical oxygen reduction reaction (ORR) in fuel cells. This work deals with the preparation of Pt nanoparticles (NPs) supported on N-doped carbon nanofibers (N-CNF) from a polyaniline nanofiber (PANI NF) precursor, and investigates the ORR activity of the produced materials. Initially, Pt NPs are deposited on PANI NFs. The PANI NF precursors are characterized by near-edge X-ray absorption fine structure (NEXAFS) and transmission electron microscopy (TEM) measurements. It is shown, that in the PANI NF precursor materials electrons from the Pt are being transferred toward the π-conjugated systems of the aromatic ring. This strong interaction of Pt atoms with PANI explains the high dispersion of Pt NPs on the PANI NF. Subsequently, the PANI NF precursors are carbonized at different heat-treatment conditions resulting in structurally different N-CNFs which are characterized by NEXAFS, X-ray photoelectron spectroscopy (XPS) ,and TEM measurements. It is shown that an interaction between N-groups and Pt NPs exists in all investigated N-CNFs. However, the N-CNFs differ in the composition of the N-species and the dispersion of the Pt NPs. A small mean Pt NP size with a narrow size distribution is attributed to the presence of pyrdinic N-groups in the N-CNFs, whereas, for the N-CNFs with mainly graphitic and pyrrolic N-groups, an increase in the average Pt NP size with a broad size distribution is found. The ORR activity in alkaline media investigated by Koutecky-Levich analysis of rotating disk electrode measurements showed a largely enhanced ORR activity in comparison to a conventional Pt/C catalyst.

  11. A New Reforming Reaction Mechanism of Carbon Dioxide with Methane on Nano Scale Nickel catalyst

    Directory of Open Access Journals (Sweden)

    Long Wei


    Full Text Available The reforming mechanism of CO2-CH4 on Nano scale Ni metal catalyst was investigated using the B3LYP density functional method and MP2/Lanl2dz method. It was found that the reaction include thirteen steps and the activation energy of each step was 44.7175, 200.4707, 171.0781, 307.2596, 124.5252, 330.7904, 593.9056, 177.5526, 226.6793, 277.789 2, 394.5525,399.5340 and 105.4115 kJ·mol−1. The rate determining step was the fourth step. The enthalpy value of each step was 31.6136, 106.7138, −104.2589, 79.9641, 93.5573,174.6 121, 259.6409, −141.9192, −439.9338, −265.4756, −208.3245, 131.6561 and −86.1765 kJ·mol−1.

  12. Reaction of erythromycin with dissolved oxygen on gold nanoparticle-modified glassy carbon electrodes

    Institute of Scientific and Technical Information of China (English)

    LI Xue; FU Ying; WANG Jian-xiu; L(U) Hui-dan; XU Mao-tian


    Cyclic voltammetry was used to investigate the reaction of erythromycin (EM) with dissolved oxygen on gold nanoparticle-modified electrodes prepared via electrodeposition. A well-defined reduction peak at -0.420 V and a reoxidation peak at -0.055V were observed. With the addition of EM into the NaOH solution containing dissolved oxygen, the oxidation peak at -0.055 V was still indiscernible. However, a new oxidation peak at 0.200V appeared, which suggests the interaction between EM and dissolved oxygen. Therefore, this method can be used for the analysis of EM in tablets. The present method is simple, reproducible,and does not require complex analytical instruments.

  13. Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide. (United States)

    Hasegawa, Jun-Ya; Miyazaki, Ray; Maeda, Chihiro; Ema, Tadashi


    Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts.

  14. Coprecipitation of (14)C and Sr with carbonate precipitates: The importance of reaction kinetics and recrystallization pathways. (United States)

    Hodkin, David J; Stewart, Douglas I; Graham, James T; Burke, Ian T


    This study investigated the simultaneous removal of Sr(2+) and (14)CO3(2-) from pH>12 Ca(OH)2 solution by the precipitation of calcium carbonate. Initial Ca(2+):CO3(2-) ratios ranged from 10:1 to 10:100 (mM:mM). Maximum removal of (14)C and Sr(2+) both occurred in the system containing 10mM Ca(2+) and 1mM CO3(2-) (99.7% and 98.6% removal respectively). A kinetic model is provided that describes (14)C and Sr removal in terms of mineral dissolution and precipitation reactions. The removal of (14)C was achieved during the depletion of the initial TIC in solution, and was subsequently significantly affected by recrystallization of the calcite precipitate from an elongate to isotropic morphology. This liberated >46% of the (14)C back to solution. Sr(2+) removal occurred as Ca(2+) became depleted in solution and was not significantly affected by the recrystallization process. The proposed reaction could form the basis for low cost remediation scheme for (90)Sr and (14)C in radioactively contaminated waters (<$0.25 reagent cost per m(3) treated).

  15. Enantioselective organocatalyzed Oxa-Michael-Aldol cascade reactions: Construction of chiral 4H-chromenes with a trifluoromethylated tetrasubstituted carbon stereocenter

    KAUST Repository

    Zhang, Jing


    The first organocatalytic asymmetric synthesis of 4H-chromenes bearing a trifluoromethylated tetrasubstituted carbon center is presented. Chiral secondary amines promote the oxa-Michael-aldol cascade reaction between alkynals and 2-trifluoroacetylphenols via iminium-allenamine activation to produce pharmaceutically important heterocycles with excellent enantioselectivities. The proposed reaction can be scaled-up easily with maintenance of the excellent enantioselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Alkali-metalated forms of thiacalix[4]arenes. (United States)

    Zeller, Jürgen; Radius, Udo


    The alkali metal salts [TCALi4] (1), [TCANa4] (2), and [TCALK4] (3) of fully deprotonated p-tert-butyltetrathiacalix[4]arene (H(4)TCA) are readily available from the reactions of thiacalix[4]arene and n-BuLi, NaH, or KH as deprotonating reagents. Crystals of the sodium salts 2 and the potassium salt 3 suitable for X-ray diffraction were obtained in the form of the pyridine solvates [(TCA)2Na8.8py] (2.8py) and [(TCA)2K(8).8py] (3.8py). These molecules are dimers in the solid state but are structurally not related. In addition, the reaction of H(4)TCA and lithium hydroxide afforded the structurally characterized complex [(TCA)Li5(OH).4THF] (4). The molecular structure of 4 as well as the structures of 2.8py and 3.8py reveal a close relationship to the corresponding alkali metal salts of the calix[4]arenes.

  17. Alkali-hydrolysis of D-glucono-delta-lactone studied by chiral Raman and circular dichroism spectroscopies

    Institute of Scientific and Technical Information of China (English)

    JIA GuoQing; QIU Shi; LI GuanNa; ZHOU Jun; FENG ZhaoChi; LI Can


    The alkali-hydrolysis of D-glucono-delta-lactone (GDL) was investigated by chiral Raman and circular dichroism (CD) spectroecopies in combination with density functional theory calculation. Based on the characteristic CD bands of GDL and its hydrolysis product, the dynamics of hydrolysis was studied using stopped-flow CD method. Using chiral Raman spectroscopy (CRS), the stereochemical change of GDL owing to the hydrolysis reaction was discussed on the vibrational scale. The CRS results show that the ring-opening due to hydrolysis has a great influence on the chiral structure around the cer-bonyl group, which was evidenced by the disappearance of the CRS band at 1735 cm-1 (C=0 stretching vibrational mode). In addition, the change of positions and intensity of CRS bands was also observed, which was ascribed to the perturbation around the C2, C3, C4 and C5 carbons due to ring-opening. It is worthy to note that the stereochemistry of C2, C3, C4 and C5 had no fundamental change during the hydrolysis reaction, which was reflected in the maintenance of the signs of the CRS bands. Our results demonstrate that in comparison with CD technique, CRS may provide more detailed structural infor-mation of chiral molecules and open up new vistas of research for chirel reactions.

  18. Alkali-hydrolysis of D-glucono-delta-lactone studied by chiral Raman and circular dichroism spectroscopies

    Institute of Scientific and Technical Information of China (English)


    The alkali-hydrolysis of D-glucono-delta-lactone (GDL) was investigated by chiral Raman and circular dichroism (CD) spectroscopies in combination with density functional theory calculation. Based on the characteristic CD bands of GDL and its hydrolysis product, the dynamics of hydrolysis was studied using stopped-flow CD method. Using chiral Raman spectroscopy (CRS), the stereochemical change of GDL owing to the hydrolysis reaction was discussed on the vibrational scale. The CRS results show that the ring-opening due to hydrolysis has a great influence on the chiral structure around the car-bonyl group, which was evidenced by the disappearance of the CRS band at 1735 cm-1 (C== O stretching vibrational mode). In addition, the change of positions and intensity of CRS bands was also observed, which was ascribed to the perturbation around the C2, C3, C4 and C5 carbons due to ring-opening. It is worthy to note that the stereochemistry of C2, C3, C4 and C5 had no fundamental change during the hydrolysis reaction, which was reflected in the maintenance of the signs of the CRS bands. Our results demonstrate that in comparison with CD technique, CRS may provide more detailed structural information of chiral molecules and open up new vistas of research for chiral reactions.

  19. Influence of curing conditions on durability of alkali-resistant glass fibres in cement matrix

    Indian Academy of Sciences (India)

    Arabi Nourredine


    Glass fibres in concrete material often increase the flexural strength. However, these fibres when in contact with cement are altered by alkali reactions due to the presence of portlandite. This study presents the results of investigation to show the effect of curing conditions on the durability of alkali-resistant glass fibres in cement matrix. Test results show that even alkali resistant fibres treated with zirconium oxide present the same degradation phenomenon. They also show that the nature of the cement has a large influence on the protection of the fibres: the Portland CEM II is less damaging than the CEM I. The substitutions of a part of cement by silica fume gave no substantial improvements to the mechanical strength of the glass fibre reinforced cement (GFRC). However, the observed microstructures in the samples show that the degradation is weakened with the addition of silica fumes. The analytical techniques used in this study are scanning electron microscope (SEM) and X-ray diffraction.

  20. Chemiluminescence behavior of sodium hydrogen carbonate in the potassium permanganate-hydrogen peroxide reaction

    Institute of Scientific and Technical Information of China (English)


    Chemiluminescence (CL) phenomenon of hydrogen peroxide with potassium permanganate in the presence of sodium hydrogen carbonate was reported.Effects of the surfactant on the CL system were investigated.Nonionic surfactants could effectively increase the CL signal.Radical scavengers and organic reagents such as nitro blue tetrazolium chloride (NBT),cytochrome c,sodium azide,ascorbic acid,thiourea,tert-butanol and dimethyl sulphoxide were used to study the emitting species.CL emission spectrum was recorded and the results showed that the maximal emission wavelengths of NaHCO3-H2O2-KMnO4 system were 440 and 634 nm.The mechanism was discussed based on electron spin resonance (ESR) spectra,fluorescence spectra and UV-vis absorption spectra.The addition of rhodamine B or uranine into this CL system enhanced the CL signal.It was due to part of the energy transfer from singlet oxygen and excited triplet dimers of two CO2 molecules to rhodamine B or uranine.The CL could be induced by excited rhodamine B or uranine.

  1. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. V. Chemical dynamics of n-C4H3 formation from reaction of C(3Pj) with allene, H2CCCH2(X 1A1) (United States)

    Kaiser, R. I.; Mebel, A. M.; Chang, A. H. H.; Lin, S. H.; Lee, Y. T.


    The crossed molecular beams technique was employed to investigate the reaction between ground state carbon atoms, C(3Pj), and allene, H2CCCH2(X 1A1), at two averaged collision energies of 19.6 and 38.8 kJ mol-1. Product angular distributions and time-of-flight spectra of C4H3 were recorded. Forward-convolution fitting of the data yields weakly polarized center-of-mass angular flux distributions isotropic at lower, but forward scattered with respect to the carbon beam at a higher collision energy. The maximum translational energy release and the angular distributions combined with ab initio and RRKM calculations are consistent with the formation of the n-C4H3 radical in its electronic ground state. The channel to the i-C4H3 isomer contributes less than 1.5%. Reaction dynamics inferred from the experimental data indicate that the carbon atom attacks the π-orbitals of the allenic carbon-carbon double bond barrierless via a loose, reactant-like transition state located at the centrifugal barrier. The initially formed cyclopropylidene derivative rotates in a plane almost perpendicular to the total angular momentum vector around its C-axis and undergoes ring opening to triplet butatriene. At higher collision energy, the butatriene complex decomposes within 0.6 ps via hydrogen emission to form the n-C4H3 isomer and atomic hydrogen through an exit transition state located 9.2 kJ mol-1 above the products. The explicit identification of the n-C4H3 radical under single collision represents a further example of a carbon-hydrogen exchange in reactions of ground state carbon atoms with unsaturated hydrocarbons. This channel opens a barrierless route to synthesize extremely reactive hydrocarbon radicals in combustion processes, interstellar chemistry, and hydrocarbon-rich atmospheres of Jupiter, Saturn, Titan, as well as Triton.

  2. Using potassium catalytic gasification to improve the performance of solid oxide direct carbon fuel cells: Experimental characterization and elementary reaction modeling


    Yu, Xiankai; Shi, Yixiang; Wang, Hongjian; Cai, Ningsheng; Li, Chen; Ghoniem, Ahmed F


    The performance of a solid oxide electrolyte direct carbon fuel cell (SO-DCFC) is limited by the slow carbon gasification kinetics at the typical operating temperatures of cell: 650–850 °C. To overcome such limitation, potassium salt is used as a catalyst to speed up the dry carbon gasification reactions, increasing the power density by five-fold at 700–850 °C. The cell performance is shown to be sensitive to the bed temperature, emphasizing the role of gasification rates and that of CO produ...

  3. Phosphorus/sulfur Co-doped porous carbon with enhanced specific capacitance for supercapacitor and improved catalytic activity for oxygen reduction reaction (United States)

    Zhou, Yao; Ma, Ruguang; Candelaria, Stephanie L.; Wang, Jiacheng; Liu, Qian; Uchaker, Evan; Li, Pengxi; Chen, Yongfang; Cao, Guozhong


    Phosphorus (P)/sulfur (S) co-doped porous carbon derived from resorcinol and furaldehyde are synthesized through one-step sol-gel processing with the addition of phosphorus pentasulfide as P and S source followed with freeze-drying and pyrolysis in nitrogen. The P/S co-doping strategy facilitates the pore size widening both in micropore and mesopore regions, together with the positive effect on the degree of graphitization of porous carbon through elimination of amorphous carbon through the formation and evaporation of carbon disulfide. As an electrode for supercapacitor application, P/S co-doped porous carbon demonstrates 43.5% improvement on specific capacitance of the single electrode compared to pristine porous carbon in organic electrolyte at a current of 0.5 mA due to the P-induced pseudocapacitive reactions. As for electrocatalytic use, promoted electrocatalytic activity and high resistance to crossover effects of oxygen reduction reaction (ORR) in alkaline media are observed after the introduction of P and S into porous carbon. After air activation, the specific capacitance of the single electrode of sample PS-pC reaches up to 103.5 F g-1 and an improved oxygen reduction current density.

  4. Suzuki-Miyaura, Mizoroki-Heck carbon-carbon coupling and hydrogenation reactions catalysed by PdII and RhI complexes containing cyclodiphosphazane cis-{tBuNP(OC6H4OMe-)}2

    Indian Academy of Sciences (India)

    Sasmita Mohanty; Maravanji S Balakrishna


    The catalytic activity of the palladium complex cis-[PdCl2{(tBuNP(OC6H4OMe-))2- }2] (2) containing cis-{tBuNP(OC6H4OMe-)}2 (1) in Suzuki-Miyaura and Mizoroki-Heck carbon-carbon cross coupling reactions is described. The compound 2 also displays very high activity in Mizoroki-Heck coupling reactions. The rhodium(I) complex [RhCl(COD){(tBuNP(OC6H4OMe-))2- }] (3) acts as an excellent catalyst for the hydrogenation of several terminal olefins.

  5. [Reaction of NO with metal oxides and urea supported on activated carbons at low temperature]. (United States)

    Cui, Hua-Fei; Li, Cai-Ting; Lu, Pei; Peng, Dun-Liang; Guo, Jing; Chen, Ling


    The catalysts were prepared by activated carbon fiber (ACF) loaded different contents of NiO and NiO-CeO2, Urea was loaded on the prepared catalysts as reductant. The experiments of selective catalytic reductions (SCR) of NO were carried out from 30 to 120 degrees C. The experiments of SEM, BET and XRD of the samples were also carried out selectively to study the catalysts properties, respectively. The experimental results showed that the loaded mass fraction of NiO could greatly affect the catalytic activity of the catalysts. 10% NiO catalyst activity and activity stability were both higher than that of the others, and it could yield about 50% removal efficiency of NO at 90 degrees C. With the loaded mass increasing, the catalytic activity was obviously decreased. And furthermore, the catalyst of 5% NiO-5% CeO2/ACF had the best catalytic activities on SCR NO and stability among the prepared NiO-CeO2/ACF catalysts, and its NO removal efficiency was over 55% at 110 degrees C. When the loaded mass increased, the similar phenomenon was observed, which was due to the decreasing of specific surface area of the catalysts. The metal oxides, loaded on ACF, were the catalytic centers in this study. Moreover, 5% CeO2-5% NiO/ACF had the highest catalytic activity than 10% CeO2/ACF and 10% NiO/ ACF. Therefore, there should be synergistic effect between CeO2 and NiO. Finally, the catalytic mechanism of SCR on NO at low temperature was discussed.

  6. Dispersion quality of amine functionalized multiwall carbon nanotubes plays critical roles in polymerase chain reaction enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Yuce, Meral, E-mail:; Budak, Hikmet [Sabanci University, Nanotechnology Research and Application Centre (Turkey)


    Impact of dispersion quality of NH{sub 2}-MWCNTs (13–18 nm in diameter with a length between 1 and 12 µm, >99 % purity) in the amplification efficiency of a random DNA oligonucleotide library (96 bp) was investigated. Amplification yield in the presence of non-filtered NH{sub 2}-MWCNT dispersion, filtered NH{sub 2}-MWCNT dispersion and surface-attached NH{sub 2}-MWCNTs was explored, and physical interactions between NH{sub 2}-MWCNTs and major PCR reagents including DNA template, wild type Taq DNA polymerase enzyme and primers were determined using high resolution polyacrylamide gel electrophoresis, dynamic light scattering, UV–Vis-NIR spectroscopy and scanning electron microscopy techniques. The results revealed that presence of NH{sub 2}-MWCNT dispersion which was sonicated, centrifuged and filtered, enhanced the total PCR efficiency up to 70 % while the presence of NH{sub 2}-MWCNT only centrifuged after sonication, inhibited the reaction significantly at similar concentrations. Furthermore, the NH{sub 2}-MWCNTs coupled covalently onto magnetic microspheres, contributed for the specificity enhancement whilst decreasing the amplification efficiency by 30 % at the maximum concentration, which suggests a removable enhancement system for sensitive applications. On the other hand, the relative hydrodynamic size distribution measurements displayed a clear difference between the filtered NH{sub 2} and non-filtered NH{sub 2}-MWCNT water dispersions, which justifies the inhibition of the amplification by the non-filtered NH{sub 2}-MWCNTs containing big agglomerates and bundles. Finally, we demonstrated that major PCR components adsorb onto the NH{sub 2}-MWCNTs with diverse affinities, and maintain their functions after adsorption, which provides a good framework to further develop tunable NH{sub 2}-MWCNT-carriers to be utilized in various nanobiotechnology and material science applications.

  7. The reaction of Pseudomonas aeruginosa cytochrome c oxidase with carbon monoxide. (United States)

    Parr, S R; Wilson, M T; Greenwood, C


    The binding of CO to ascorbate-reduced Pseudomonas cytochrome oxidase was investigated by static-titration, stopped-flow and flash-photolytic techniques. Static-titration data indicated that the binding process was non-stoicheiometric, with a Hill number of 1.44. Stopped-flow kinetics obtained on the binding of CO to reduced Pseudomonas cytochrome oxidase were biphasic in form; the faster rate exhibited a linear dependence on CO concentration with a second-order rate constant of 2 X 10(4) M-1-s-1, whereas the slower reaction rapidly reached a pseudo-first-order rate limit at approx. 1s-1. The relative proportions of the two phases observed in stopped-flow experiments also showed a dependency on CO concentration, the slower phase increasing as the CO concentration decreased. The kinetics of CO recombination after flash-photolytic dissociation of the reduced Pseudomonas cytochrome oxidase-CO complex were also biphasic in character, both phases showing a linear pseudo-first-order rate dependence on CO concentration. The second-order rate constants were determined as 3.6 X 10(4)M-1-s-1 and 1.6 X 10(4)M-1-s-1 respectively. Again the relative proportions of the two phases varied with CO concentration, the slower phase predominating at low CO concentrations. CO dissociation from the enzyme-CO complex measured in the presence of O2 and NO indicated the presence of two rates, of the order of 0.03s-1 and 0.15s-1. When sodium dithionite was used as a reducing agent for the Pseudomonas cytochrome oxidase, the CO-combination kinetics observed by both stopped flow and flash photolysis were extremely complex and not able to be simply analysed.

  8. An experimental investigation of multiple sulfur isotope fractionations during heterogenous reactions between SO2 and activated carbon (United States)

    Hamasaki, H.; Watanabe, Y.; Ohmoto, H.


    Watanabe et al. (2009) reported that the reduced-S species produced from reactions between solid organic compounds and aqueous sulfate at 150-200 °C possessed anomalous isotopic fractionation (AIF) of S: Δ33S = 0.1 to 2.1 ‰. Based partly on these data, they suggested that the AIF-S signatures in some sedimentary rocks were produced during thermochemical sulfate reduction by solid organic compounds during the early stage of sediment diagenesis, rather than by atmospheric UV photolysis of volcanic SO2. Theoretical study by Lasaga et al. (2008) also suggested that variable AIF-S signatures could be generated during chemisorption of aqueous (or gaseous) S species on a solid surface (e.g., kerogen) under certain conditions. The main objective of this study was, therefore, to evaluate S isotope effects during different stages of reactions (e.g., adsorption, redox reactions) between a solid organic compound and SO2. We have conducted several series of experiments in a closed pyrex-glass system. About 1.8 gm (0.15 moles) of activated C (0.25-1.0 mm in diameter) was first evacuated at 300 °C for 5 days. Then 2.5 mmoles of pure SO2 gas was introduced in the system to react with activated carbon at 200 or 250 °C. Once the pSO2 became stabilized (typically after ~1 day), an aliquot of the SO2 gas (0.1 to 1.5 mmoles) was withdrawn into a pyrex-glass tube containing 20 % H2O2 solution to collect the SO2 as sulfate. After the pSO2 reached to a new steady value, another aliquot of SO2 was withdrawn from the system; sampling was continued until the amount of SO2 gas in the system decreased to 5 % of the initial value. The collected sulfate was converted to Ag2S for isotope analysis. After a series of experiment at 200 °C and another at 250 °C, the activated carbon was removed from the reaction system, treated sequentially by different chemical solutions to extract different forms of S compounds; the extracted S compounds were analyzed for their contents and isotopic ratios

  9. Systematic variation of the sodium/sulfur promoter content on carbon-supported iron catalysts for the Fischer-Tropsch to olefins reaction

    NARCIS (Netherlands)

    Oschatz, M.; Krans, N.A.; Xie, J.; de Jong, K.P.


    The Fischer–Tropsch to olefins (FTO) process is a method for the direct conversion of synthesis gas to lower C2–C4 olefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction. The catalytic activity can be improved and undesired formation of alkanes can be suppres

  10. Effect of UV and electrochemical surface treatments on the adsorption and reaction of linear alcohols on non-porous carbon fibre (United States)

    Osbeck, S.; Ward, S.; Idriss, H.


    The adsorption properties of untreated, electrochemically treated and ultra-violet/ozone treated polyacrylonitrile based carbon fibres were investigated using temperature programmed desorption (TPD) on a series of linear alcohols as probes in order to understand its surface properties. Surface uptake was found to be sensitive to both the surface treatment and the nature of the adsorbates. Surface coverage increased with increasing alcohol chain due to the increase in their polarizability. It also increased with the level of surface oxygen of the fibres most likely because it facilitates the Osbnd H bond dissociation of the alcohol functional group. In addition, the desorption temperature (during TPD) tracked the surface oxygen levels (as determined from XPS O1s signal) suggesting increasing in the adsorption energy. The reactions of C1-C4 linear alcohols were also investigated on the surface of the fibre carbon. The main reaction was dehydrogenation to the corresponding aldehydes; the dehydration reaction to olefins was not observed. The dehydrogenation reaction was sensitive to the length of the alky chain. It was highest for methanol (to formaldehyde) and decreased with increasing the carbon number. Overall TPD of linear alcohols was shown to be a promising method for quantifying the level and strength of bonding occurring on carbon fibre surfaces.

  11. Single-walled carbon nanotubes as nano-electrode and nano-reactor to control the pathways of a redox reaction. (United States)

    McSweeney, Robert L; Chamberlain, Thomas W; Davies, E Stephen; Khlobystov, Andrei N


    Single-walled carbon nanotubes have been demonstrated as effective nanoscale containers for a redox active organometallic complex Cp(Me)Mn(CO)3, acting simultaneously as nano-electrode and nano-reactor. Extreme spatial confinement of the redox reaction within the nanotubes changes its pathway compared to bulk solution due to stabilisation of a reactive intermediate.

  12. Developments in Analytical Chemistry: Acoustically Levitated Drop Reactors for Enzyme Reaction Kinetics and Single-Walled Carbon Nanotube-Based Sensors for Detection of Toxic Organic Phosphonates (United States)

    Field, Christopher Ryan


    Developments in analytical chemistry were made using acoustically levitated small volumes of liquid to study enzyme reaction kinetics and by detecting volatile organic compounds in the gas phase using single-walled carbon nanotubes. Experience gained in engineering, electronics, automation, and software development from the design and…

  13. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed

    Energy Technology Data Exchange (ETDEWEB)

    Gaikwad, Vaibhav [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Kennedy, Eric, E-mail: [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Mackie, John [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Holdsworth, Clovia [Centre for Organic Electronics, Chemistry Building, School of Environmental and Life Sciences, University of Newcastle, Callaghan, NSW 2308 (Australia); Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Dlugogorski, Bogdan [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia)


    Highlights: • CCl{sub 4} remediation using non-equilibrium plasma and non-oxidative conditions is proposed. • The reaction mechanism relies on experimental data and quantum chemical analysis. • Comprehensive mass balance for the reaction is provided. • CCl{sub 4} is converted to an environmentally benign and potentially useful polymer. • Characterisation of the polymer structure based on NMR and FTIR analyses is presented. - Abstract: In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  14. Mechanistic studies of the copolymerization reaction of oxetane and carbon dioxide to provide aliphatic polycarbonates catalyzed by (Salen)CrX complexes. (United States)

    Darensbourg, Donald J; Moncada, Adriana I; Choi, Wonsook; Reibenspies, Joseph H


    Chromium salen derivatives in the presence of anionic initiators have been shown to be very effective catalytic systems for the selective coupling of oxetane and carbon dioxide to provide the corresponding polycarbonate with a minimal amount of ether linkages. Optimization of the chromium(III) system was achieved utilizing a salen ligand with tert-butyl groups in the 3,5-positions of the phenolate rings and a cyclohexylene backbone for the diimine along with an azide ion initiator. The mechanism for the coupling reaction of oxetane and carbon dioxide has been studied. Based on binding studies done by infrared spectroscopy, X-ray crystallography, kinetic data, end group analysis done by (1)H NMR, and infrared spectroscopy, a mechanism of the copolymerization reaction is proposed. The formation of the copolymer is shown to proceed in part by way of the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction, and by the direct enchainment of oxetane and CO 2. The parity of the determined free energies of activation for these two processes, namely 101.9 kJ x mol (-1) for ring-opening polymerization of trimethylene carbonate and 107.6 kJ x mol (-1) for copolymerization of oxetane and carbon dioxide supports this conclusion.

  15. Controlled Reactions between Ultracold Alkali and Metastable Helium Atoms

    CERN Document Server

    Flores, Adonis Silva; Knoop, Steven


    In an ultracold, optically trapped mixture of $^{87}$Rb and metastable triplet $^4$He atoms we have studied trap loss for different spin-state combinations, for which interspecies Penning ionization is the main two-body loss process. We observe long trapping lifetimes for the purely quartet spin-state combination, indicating strong suppression of Penning ionization loss by at least two orders of magnitude. For the other spin-mixtures we observe short lifetimes that depend linearly on the doublet character of the entrance channel. We compare the extracted loss rate coefficient with recent predictions of multichannel quantum-defect theory for reactive collisions involving a strong exothermic loss channel and find near-universal loss for doublet scattering. Our work demonstrates control of reactive collisions by internal atomic state preparation, which also implies magnetic field tunability.

  16. A Novel One-Pot and One-Step Microwave-Assisted Cyclization-Methylation Reaction of Amino Alcohols and Acetylated Derivatives with Dimethyl Carbonate and TBAC (United States)

    Ochoa-Terán, Adrián; Guerrero, Leticia; Rivero, Ignacio A.


    A simple and efficient microwave-assisted methodology for the synthesis of 4-substituted-3-methyl-1,3-oxazolidin-2-ones from amino alcohols catalyzed by a ionic liquid was developed. This novel one-pot and one-step cyclization-methylation reaction represents an easier and faster method than any other reported protocols that can be used to obtain the desired products in good yields and high purity. Applying microwave irradiation at 130°C in the presence of TBAC, dimethyl carbonate acts simultaneously as carbonylating and methylating agent and surprisingly promotes an in situ basic trans esterification when a N-acetylated amino alcohol is used as starting material. Furthermore, dimethyl carbonate worked better than diethyl carbonate in performing this reaction. PMID:25692177

  17. Reaction-induced porosity and onset of low-temperature carbonation in abyssal peridotites: Insights from 3D high-resolution microtomography (United States)

    Jöns, Niels; Kahl, Wolf-Achim; Bach, Wolfgang


    In a drillcore sample of serpentinized harzburgite from the uppermost oceanic crust (Mid-Atlantic Ridge, ODP Leg 209, Site 1270), we demonstrate using high-resolution 3D-microtomography that micron-sized open cavities are present. The development of porosity is interpreted to result from dissolution of brucite and/or olivine. Petrographic observations indicate that voids are integrated in a network of carbonate veins, the formation of which is linked to changing alkalinity in conjunction with dissolution reactions. Partial carbonate filling of pore spaces indicates that under static conditions low-temperature carbonation leads to clogging of fluid pathways and thus to a reduction in permeability. Electron microprobe analyses show that the inner walls of open voids are lined with Fe-rich precipitates. We propose that the iron in those phases was released by brucite or olivine dissolution and was subsequently oxidized and precipitated as ferric hydroxide. Thermodynamic computations show that this process may be a potential source of catabolic energy for microorganisms inhabiting serpentinites. The proposed carbonation mechanism implies that carbonate precipitation may start soon after exposure of the abyssal peridotites, when dissolution of brucite and weathering of olivine begin, and continue until the phases become inaccessible to seawater. Predicting carbonation rates of abyssal peridotites will hence require understanding of permeability reactions.

  18. High and rapid alkali cation storage in ultramicroporous carbonaceous materials (United States)

    Yun, Young Soo; Lee, Seulbee; Kim, Na Rae; Kang, Minjee; Leal, Cecilia; Park, Kyu-Young; Kang, Kisuk; Jin, Hyoung-Joon


    To achieve better supercapacitor performance, efforts have focused on increasing the specific surface area of electrode materials to obtain higher energy and power density. The control of pores in these materials is one of the most effective ways to increase the surface area. However, when the size of pores decreases to a sub-nanometer regime, it becomes difficult to apply the conventional parallel-plate capacitor model because the charge separation distance (d-value) of the electrical double layer has a similar length scale. In this study, ultramicroporous carbonaceous materials (UCMs) containing sub-nanometer-scale pores are fabricated using a simple in situ carbonization/activation of cellulose-based compounds containing potassium. The results show that alkali cations act as charge carriers in the ultramicropores (<0.7 nm), and these materials can deliver high capacitances of ∼300 F g-1 at 0.5 A g-1 and 130 F g-1, even at a high current rate of 65 A g-1 in an aqueous medium. In addition, the UCM-based symmetric supercapacitors are stable over 10,000 cycles and have a high energy and power densities of 8.4 Wh kg-1 and 15,000 W kg-1, respectively. This study provides a better understanding of the effects of ultramicropores in alkali cation storage.

  19. Mechanical and microstructural properties of alkali-activated fly ash geopolymers. (United States)

    Komljenović, M; Bascarević, Z; Bradić, V


    This paper investigates the properties of geopolymer obtained by alkali-activation of fly ash (FA), i.e. the influence of characteristics of the representative group of FA (class F) from Serbia, as well as that of the nature and concentration of various activators on mechanical and microstructural properties of geopolymers. Aqueous solutions of Ca(OH)(2), NaOH, NaOH+Na(2)CO(3), KOH and sodium silicate (water glass) of various concentrations were used as alkali activators. It was established that the nature and concentration of the activator was the most dominant parameter in the alkali-activation process. In respect of physical characteristics of FA, the key parameter was fineness. The geopolymer based on FA with the highest content of fine particles (<43 microm), showed the highest compressive strength in all cases. Regardless of FA characteristics, nature and concentration of the activator, the alkali-activation products were mainly amorphous. The formation of crystalline phases (zeolites) occurred in some cases, depending on the reaction conditions. The highest compressive strength was obtained using sodium silicate. Together with the increase of sodium silicate SiO(2)/Na(2)O mass ratio, the atomic Si/Al ratio in the reaction products was also increased. Under the experimental conditions of this investigation, high strength was directly related to the high Si/Al ratio.

  20. 碱减量废水处理技术研究%Study of Treatment Technology for Wastewater from Alkali - Decrement

    Institute of Scientific and Technical Information of China (English)

    詹伯君; 戴林富


    印染厂排放的碱减量废水,CODcr和碱含量很高。利用工业废酸、废铁屑和电石渣,研究了印染碱减量废水处理新工艺,对酸析pH点、铁炭反应时间、生物膜法SBR和活性污泥SBR处理效果进行了探讨,结果表明:在酸析点pH 3~4时,CODcr去除率大于72%;铁碳反应时间20~30 min,COD去除率大于62%;生物膜法SBR工艺的处理效果比活性污泥法SBR工艺好。%The CODcr and alkali content in the wastewater discharged fion printing and dyeing mills are very high. Anew process was tested for the treatment of the wastewater from alkali - decrement in a printing and dyeing mill usingindustrial spent acid, scrap iron and carbide slag. The pH value range of acid eduction, the iron-carbon reaction time and the results of the treatment using biological membrane SBR (sequencing batch reactor) process and activated sludge SBRprocess were studied. The results showed that the CODcr removal rate exceeded 72% when the pH value range of acideduction was 3~4; the CODcr removal rate exceeded 62% when the iron-carbon reaction time was 20~30 min; thetreatment result by biological mcmbrane SBR process vas better than the result by activated sludge SBR process.

  1. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.


    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  2. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.


    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  3. A kinetic study on the adsorption and reaction of hydrogen over silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    VanderWiel, D.P.


    Although the catalytic hydrogenation of carbon monoxide has been a subject of considerable investigation for many years, its increasing economical attractiveness as an industrial source of hydrocarbons has recently led to a search for more active and selective catalysts. A fundamental problem in the development of such catalysts is an incomplete knowledge of the operative surface processes, due in large part to the inability to accurately measure surface concentrations of reactant species during reaction. Specifically, the concentration of surface hydrogen proves difficult to estimate using normally revealing techniques such as transient isotopic exchange due to kinetic isotope effects. Knowledge of such concentrations is essential to the determination of the mechanisms of adsorption and reaction, since many kinetic parameters are concentration dependent. It is the aim of this research to investigate the mechanism and kinetics of the adsorption and reaction of hydrogen on silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide. By preadsorbing carbon monoxide onto the surface of ruthenium and silver-ruthenium catalysts, the kinetics of hydrogen adsorption and reaction can be monitored upon exposure of this surface to ambient hydrogen gas. This is accomplished by conducting identical experiments on two separate systems. First, the formation of methane is monitored using mass spectroscopy, and specific reaction rates and apparent activation energies are measured. Next, in situ {sup 1}H-NMR is used to monitor the amount of hydrogen present on the catalyst surface during adsorption and reaction. The results for these two sets of experiments are then combined to show a correlation between the rate of reaction and the surface hydrogen concentration. Finally, transition state theory is applied to this system and is used to explain the observed change in the apparent activation energy. The structure sensitivity of hydrogen

  4. Microstructural and Mechanical Properties of Alkali Activated Colombian Raw Materials

    Directory of Open Access Journals (Sweden)

    Maria Criado


    Full Text Available Microstructural and mechanical properties of alkali activated binders based on blends of Colombian granulated blast furnace slag (GBFS and fly ash (FA were investigated. The synthesis of alkali activated binders was conducted at 85 °C for 24 h with different slag/fly ash ratios (100:0, 80:20, 60:40, 40:60, 20:80, and 0:100. Mineralogical and microstructural characterization was carried out by means of X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR, Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX and Nuclear magnetic resonance (NMR. Mechanical properties were evaluated through the compressive strength, modulus of elasticity and Poisson’s ratio. The results show that two different reaction products were detected in the slag/fly ash mixtures, a calcium silicate hydrate with Al in its structure (C-A-S-H gel and a sodium aluminosilicate hydrate (N-A-S-H gel with higher number of polymerized species and low content in Ca. It was found that with the increase of the amount of added slag, the amount of C-A-S-H gel increased and the amount of N-A-S-H gel decreased. The matrix was more dense and compact with almost absence of pores. The predominance of slag affected positively the compressive strength, Young’s modulus and Poisson’s ratio, with 80% slag and 20% fly ash concrete being the best mechanical performance blend.

  5. Positronium impact ionization of Alkali atoms

    CERN Document Server

    Ghosh, D


    Target ionization processes of alkali atoms by Positronium impact are investigated. Calculations are performed in the frame work of model potential formalism using the Coulomb distorted eikonal approximation. Interesting qualitative features are noted both in the scattered Ps and the ejected electron distributions in differential as well as double differential levels of the collision cross sections.

  6. A Computational Study on the Mechanism for the K_2CO_3-catalyzed Reaction of Carbon Dioxide and 1-Chlo-2-propanol

    Institute of Scientific and Technical Information of China (English)

    张福兰; 万邦江; 黄辉胜


    The microcosmic reaction mechanism of K2CO3-catalyzed 1-chlo-2-propanol and carbon dioxide has been investigated by density functional theory(DFT) at the GGA/PW91/DNP level.We optimize the geometric configurations of reactants,intermediates,transition states,and products.The energy analysis calculation approves the authenticity of intermediates and transition states.According to our calculations,four feasible reaction pathways are found.The main pathway of the reaction is ReA → IMA1 → TSA1 → IMA2 → IMA5 → TSA5 → P.Besides,we also in-vestigate the reaction mechanism of 1-chlo-2-propanol and carbon dioxide without K2CO3-catalyzation by the same theory and level.The computational results indicate that the activation barrier with K2CO3-catalyzed is smaller than the activation barrier without K2CO3-catalyzed.That is to say,K2CO3 can promote the reaction to give the product in a high yield,which is in agreement with the experimental results.

  7. Chemical Reaction CO+OH(•) → CO2+H(•) Autocatalyzed by Carbon Dioxide: Quantum Chemical Study of the Potential Energy Surfaces. (United States)

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S


    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing.

  8. Preparation of sodium bichromate dihydrate by hydrothermal oxidizing reaction%碳素铬铁水热法制红矾钠

    Institute of Scientific and Technical Information of China (English)



    在碳素铬铁水热法制铬酸钠的基础上,充分利用二氧化碳的酸化、催化作用,可在不增添设备和原料的情况下,使反应产物由含少量游离碱的铬酸钠碱性液,转变为含少量铬酸钠的重铬酸钠溶液,同时碱耗下降1/3.该反应可用纯碱代替烧碱.结果表明,采用炉料铬粉水热反应制得的红矾钠成本可望低于铬铁矿焙烧法的成本.%Based on hydrothermal oxidizing reaction of high content carbon ferrochrome for manufacturing sodium chromate, the reaction product sodium chromate alkaline solution containing a small amount of free alkali was converted into sodium bichromate solution containing a small amount of sodium chromate,and meanwhile alkali consumption declined by 1/3,by taking full advantage of acidification and catalytic effect of carbon dioxide, and without adding equipment and raw material. Soda can be used to replace caustic soda in the reaction.Experiment results showed that sodium bichromate cost of applying high content carbon ferrochrome powder hydrothermal oxidizing reaction promises to be less than that of high-temperature chromite roasting.

  9. Mechanical Properties and Eco-Efficiency of Steel Fiber Reinforced Alkali-Activated Slag Concrete


    Sun-Woo Kim; Seok-Joon Jang; Dae-Hyun Kang; Kyung-Lim Ahn; Hyun-Do Yun


    Conventional concrete production that uses ordinary Portland cement (OPC) as a binder seems unsustainable due to its high energy consumption, natural resource exhaustion and huge carbon dioxide (CO2) emissions. To transform the conventional process of concrete production to a more sustainable process, the replacement of high energy-consumptive PC with new binders such as fly ash and alkali-activated slag (AAS) from available industrial by-products has been recognized as an alternative. This p...

  10. In situ monitoring of the acetylene decomposition and gas temperature at reaction conditions for the deposition of carbon nanotubes using linear Raman scattering. (United States)

    Reinhold-López, Karla; Braeuer, Andreas; Popovska, Nadejda; Leipertz, Alfred


    To understand the reaction mechanisms taking place by growing carbon nanotubes via the catalytic chemical vapor deposition process, a strategy to monitor in situ the gas phase at reaction conditions was developed applying linear Raman spectroscopy. The simultaneous determination of the gas temperature and composition was possible by a new strategy of the evaluation of the Raman spectra. In agreement to the well-known exothermic decomposition of acetylene, a gas temperature increase was quantified when acetylene was added to the incident flow. Information about exhaust gas recirculation and location of the maximal acetylene conversion was derived from the composition measurements.

  11. Low-temperature intermediates to oxygen reduction reaction catalysts based on amine-modified metal-loaded carbons. An XPS and ss-NMR investigation

    Energy Technology Data Exchange (ETDEWEB)

    Marzorati, Stefania [Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19, 20133 Milano (Italy); Ragg, Enzio M. [Università degli Studi di Milano, Dipartimento di Scienze per l’Alimentazione, la Nutrizione e l’Ambiente, Via Celoria, 2, 20133 Milano (Italy); Longhi, Mariangela, E-mail: [Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19, 20133 Milano (Italy); Formaro, Leonardo [Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19, 20133 Milano (Italy)


    Carbon functionalization is a major subject of interest in a number of project applications. Herein we report results on the characterization of nitrogen- and metal-loaded (Me = Fe, Co) carbon derivatives from low-T reaction steps before they are converted to catalysts for electrochemical oxygen reduction by later high-T treatments. The aim is to shed light on the state of carbon and carbon-bonded moieties before thermal modifications take place during any chosen high-T treatment. Though necessary for end catalyst activation, such thermal treatments make difficult to establish a relation between the starting reactants and finally obtained catalysts. Of interest to the paper are {sup 13}C, {sup 15}N solid-state NMR (ss-NMR) and high-resolution X-ray Photoelectron Spectroscopy (XPS) results on a commercial carbon that was reacted first with aliphatic di- and tri-amines and then with Fe, Co ions in room-T water. Data from natural abundance ss-{sup 15}N NMR in combination with XPS analysis were found especially relevant to assess that, in the adopted conditions, amines preferentially bind to carbon by creating alkylimino functional groups, which spontaneously form hydrous surface metal complexes with soluble Fe and Co ions. A chemical model is thus proposed for metal coordination in such C–N species. - Highlights: • A commercial carbon is nitrogen-doped by a low-T reaction with di- and tri-amines. • In the used conditions alkylimino groups are formed, able to act as ligands with metals (mainly Co). • A combination of {sup 13}C, {sup 15}N NMR and XPS is adopted for product characterization. • A model is proposed for the metal coordination with surface bonded groups.

  12. Chlorate reduction in the brine circuit of a chlor-alkali electrolysis. Chlorat-Reduktion im Solekreislauf einer Chlor-Alkali-Elektrolyse

    Energy Technology Data Exchange (ETDEWEB)

    Rodermund, R.


    The influence of reactant concentrations and temperature on the rate and selectivity of the chlorate/hydrochloric acid reaction was determined experimentally. A model equation system was derived on the basis of a reaction mechanism describing the reaction between chlorate and hydrochloric acid at high H/sup +/ and Cl/sup -/ concentrations in the temperature range between 40 and 90/sup 0/C. The reaction of chlorate and hydrochloric acid was found to be sufficient to maintain a low chlorate level in the brine circuit of a chlor-alkali electrolysis. ClO/sub 2/ formation is negligible if suitable reaction conditions are chosen. Further, a model equation based on Henry's law was established for the solubility of ClO/sub 2/ in mixed solutions of HCl and NaCl in the temperature range of 40 to 90/sup 0/C.

  13. Nouvelle approche pour le suivi de la réactivité de phases SiO2 soumises à la Réaction Alcali Silice (RAS New approach for monitoring the reactivity of SiO2 phases subject to Alkali Silica Reaction (SAR

    Directory of Open Access Journals (Sweden)

    Harfouche M.


    Full Text Available Nous avons suivi- au moyen de la microscopie électronique à balayage environnementale (MEBE la diffraction X et la spectroscopie d’absorption des rayons X sous rayonnement synchrotron (XANES- la réactivité de certaines phases SiO2 lors du processus de la Réaction Alcali Silice (RAS. Cette réactivité est étroitement liée à la structure locale autour des atomes de silicium ainsi qu’à la présence d’impuretés comme le fer. Dans le cas du silex brut, la raie blanche du seuil K du fer ressemble davantage à celle de Fe3O4 ce qui permet de déduire la présence d’un mélange de Fe2+/Fe3+ dans le silex de départ. Après réaction, l’allure du spectre d’absorption des rayons X au seuil K du fer du silex est conservée avec un léger déplacement de la raie blanche vers les hautes énergies. Cette augmentation montre une prédominance de la valence Fe3+ au détriment de la valence Fe2+. Les résultats montrent que le fer participe à la stabilisation de la structure des phases formées. Cette étude peut être étendue à d’autres éléments traces présents dans la structure du silex de départ. In this study the reactivity of some SiO2 phases under Alkali Silica Reaction (RAS process is followed, using the environmental scanning electron microscopy (ESEM X-ray diffraction and absorption spectroscopy X-ray synchrotron radiation (XANES. This reactivity is closely related to the local structure around the silicon atoms and the presence of impurities such as iron. In the case of flint raw skate white iron K line is more like that of Fe3O4 which allows to deduce the presence of a mixture of Fe2+ / Fe3+ in the flint to start. After reaction, the shape of the spectrum of X-ray absorption K edge of iron in the flint is retained with a slight displacement of the white stripe to high energies. This increase shows a predominance of the valence Fe3+ at the expense of Fe2+ valence. The results show that iron is involved in stabilizing the

  14. Theory of metal atom-water interactions and alkali halide dimers (United States)

    Jordan, K. D.; Kurtz, H. A.


    Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

  15. Alkali-Resistant Quasi-Solid-State Electrolyte for Stretchable Supercapacitors. (United States)

    Tang, Qianqiu; Wang, Wenqiang; Wang, Gengchao


    Research on stretchable energy-storage devices has been motivated by elastic electronics, and considerable research efforts have been devoted to the development of stretchable electrodes. However, stretchable electrolytes, another critical component in stretchable devices, have earned quite little attention, especially the alkali-resistant ones. Here, we reported a novel stretchable alkali-resistant electrolyte made of a polyolefin elastomer porous membrane supported potassium hydroxide-potassium polyacrylate (POE@KOH-PAAK). The as-prepared electrolyte shows a negligible plastic deformation even after 1000 stretching cycles at a strain of 150% as well as a high conductivity of 0.14 S cm(-1). It also exhibits excellent alkali resistance, which shows no obvious degradation of the mechanical performance after immersion in 2 M KOH for up to 2 weeks. To demonstrate its good properties, a high-performance stretchable supercapacitor is assembled using a carbon-nanotube-film-supported NiCo2O4 (CNT@NiCo2O4) as the cathode and Fe2O3 (CNT@Fe2O3) as the anode, proving great application promise of the stretchable alkali-resistant electrolyte in stretchable energy-storage devices.

  16. Plasma assisted measurements of alkali metal concentrations in pressurized combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Hernberg, R.; Haeyrinen, V. [Tampere Univ. of Technology (Finland). Dept. of Physics


    The plasma assisted method for continuous measurement of alkali concentrations in product gas flows of pressurized energy processes will be tested and applied at the 1.6 MW PFBC/G facility at Delft University of Technology in the Netherlands. During the reporting period the alkali measuring device has been tested under pressurized conditions at VTT Energy, DMT, Foster-Wheeler Energia and ABB Carbon. Measurements in Delft will be performed during 1996 after installation of the hot gas filter. The original plan for measurements in Delft has been postponed due to schedule delays in Delft. The results are expected to give information about the influence of different process conditions on the generation of alkali vapours, the comparison of different methods for alkali measurement and the specific performance of our system. This will be the first test of the plasma assisted measurement method in a gasification process. The project belongs to the Joule II extension program under contract JOU2-CT93-0431. (author)

  17. Superconductivity and electrical resistivity in alkali metal doped fullerides: Phonon mechanism

    Indian Academy of Sciences (India)

    Dinesh Varshney; A Dube; K K Choudhary; R K Singh


    We consider a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. We first study the intercage interactions between the adjacent C60 cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C60 phonons. Electronic parameter as repulsive parameter and the attractive coupling strength are obtained within the random phase approximation. Transition temperature, c, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C60 phonons as 5 K, which is much lower as compared to reported c (≈ 20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. To illustrate the usefulness of the above approach, the carbon isotope exponent and the pressure effect are also estimated. Temperature dependence of electrical resistivity is then analysed within the same model phonon spectrum. It is inferred from the two-peak model for phonon density of states that high frequency intramolecular phonon modes play a major role in pairing mechanism with possibly some contribution from alkali-C60 phonon to describe most of the superconducting and normal state properties of doped fullerides.

  18. Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning NMR Spectroscopy (United States)

    Hu, J.; Kwak, J.; Hoyt, D. W.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.


    Ex situ solid state NMR have been used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration using a model silicate mineral forsterite (Mg2SiO4)+scCO2 with and without H2O. Run conditions were 80C and 96 bar. Si-29 NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce Mg2+, and mono- and oligomeric hydroxylated silica species. The surface hydrolysis products contain only Q0 (Si(OH)4) and Q1 (Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. Si-29 NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. C-13 MAS NMR identified a possible reaction intermediates as (MgCO3)4*Mg(OH)2*5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed. This research is part of a broader effort at PNNL to develop experimental tools and fundamental insights into chemical transformations affecting subsurface CO2 reactive transport. Si-29 (left) and C-13 (right) MAS NMR spectra of Mg2SiO4 under various reaction conditions. Si-29 NMR reveals that in scCO2 without H2O, no reaction is

  19. Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles. (United States)

    Trillo, Paz; Baeza, Alejandro; Nájera, Carmen


    The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.

  20. Metal-free N-doped carbon nanofibers as an efficient catalyst for oxygen reduction reactions in alkaline and acid media (United States)

    Li, Ruchun; Shao, Xiaofeng; Li, Shuoshuo; Cheng, Pengpeng; Hu, Zhaoxia; Yuan, Dingsheng


    The development of metal-free catalysts to replace the use of Pt has played an important role in relation to its application to fuel cells. We report N-doped carbon nanofibers as the catalyst of an oxygen reduction reaction, which were synthesized via carbonizing bacterial cellulose-polypyrrole composites. The as-prepared material exhibited remarkable catalytic activity toward the oxygen reduction reaction with comparable onset potential and the ability to limit the current density of commercial Pt/C catalysts in both alkaline and acid media due to the unique porous three-dimensional network structure and the doped nitrogen atoms. The effect of N functionalities on catalytic behavior was systematically investigated. The results demonstrated that pyridinic-N was the dominating factor for catalytic performance toward the oxygen reduction reaction. Additionally, N-doped carbon nanofibers also demonstrated excellent cycling stability (93.2% and 89.4% retention of current density after chronoamperometry 20 000 s in alkaline and media, respectively), obviously superior to Pt/C.

  1. Structural and Magnetic Diversity in Alkali-Metal Manganate Chemistry: Evaluating Donor and Alkali-Metal Effects in Co-complexation Processes. (United States)

    Uzelac, Marina; Borilovic, Ivana; Amores, Marco; Cadenbach, Thomas; Kennedy, Alan R; Aromí, Guillem; Hevia, Eva


    By exploring co-complexation reactions between the manganese alkyl Mn(CH2SiMe3)2 and the heavier alkali-metal alkyls M(CH2SiMe3) (M=Na, K) in a benzene/hexane solvent mixture and in some cases adding Lewis donors (bidentate TMEDA, 1,4-dioxane, and 1,4-diazabicyclo[2,2,2] octane (DABCO)) has produced a new family of alkali-metal tris(alkyl) manganates. The influences that the alkali metal and the donor solvent impose on the structures and magnetic properties of these ates have been assessed by a combination of X-ray, SQUID magnetization measurements, and EPR spectroscopy. These studies uncover a diverse structural chemistry ranging from discrete monomers [(TMEDA)2 MMn(CH2SiMe3)3] (M=Na, 3; M=K, 4) to dimers [{KMn(CH2SiMe3)3 ⋅C6 H6}2] (2) and [{NaMn(CH2SiMe3)3}2 (dioxane)7] (5); and to more complex supramolecular networks [{NaMn(CH2SiMe3)3}∞] (1) and [{Na2Mn2 (CH2SiMe3)6 (DABCO)2}∞] (7)). Interestingly, the identity of the alkali metal exerts a significant effect in the reactions of 1 and 2 with 1,4-dioxane, as 1 produces coordination adduct 5, while 2 forms heteroleptic [{(dioxane)6K2Mn2 (CH2SiMe3)4(O(CH2)2OCH=CH2)2}∞] (6) containing two alkoxide-vinyl anions resulting from α-metalation and ring opening of dioxane. Compounds 6 and 7, containing two spin carriers, exhibit antiferromagnetic coupling of their S=5/2 moments with varying intensity depending on the nature of the exchange pathways.

  2. Synthesis and Selective Coloration of Monoaza Crown Ethers Bearing Picrylamino-type Side Arms for Alkali Metal Salts and Methylamine

    Institute of Scientific and Technical Information of China (English)

    Wei ZENG; Zhi Hua MAO; Mi GONG; Chun Chun ZHANG; Sheng Ying QIN; Jun SU


    N-pivot lariat ethers with picrylamino group as a chromophore (1, 2 and 3) have been prepared by reaction of N-(4-aminoaryl)monoaza crown ethers with picryl chrolide, and the selective coloration of 1, 2 and 3 for alkali metal salts and amines has been studied by UV-Vis spectra.

  3. PFB air gasification of biomass. Investigation of product formation and problematic issues related to ammonia, tar and alkali

    Energy Technology Data Exchange (ETDEWEB)

    Padban, Nader


    Fluidised bed thermal gasification of biomass is an effective route that results in 100 % conversion of the fuel. In contrast to chemical, enzymatic or anaerobic methods of biomass treatment, the thermal conversion leaves no contaminated residue after the process. The product gas evolved within thermal conversion can be used in several applications such as: fuel for gas turbines, combustion engines and fuel cells, and raw material for production of chemicals and synthetic liquid fuels. This thesis treats a part of the experimental data from two different gasifiers: a 90 kW{sub th} pressurised fluidised bubbling bed gasifier at Lund University and a 18 MW{sub th} circulating fluidised bed gasifier integrated with gas turbine (IGCC) in Vaernamo. A series of parallel and consecutive chemical reactions is involved in thermal gasification, giving origin to formation of a variety of products. These products can be classified within three major groups: gases, tars and oils, and char. The proportion of these categories of species in the final product is a matter of the gasifier design and the process parameters. The thesis addresses the technical and theoretical aspects of the biomass thermochemical conversion and presents a new approach in describing the gasification reactions. There is an evidence of fuel effect on the characteristics of the final products: a mixture of plastic waste (polyethylene) and biomass results in higher concentration of linear hydrocarbons in the gas than gasification of pure biomass. Mixing the biomass with textile waste (containing aromatic structure) results in a high degree of formation of aromatic compounds and light tars. Three topic questions within biomass gasification, namely: tar, NO{sub x} and alkali are discussed in the thesis. The experimental results show that gasification at high ER or high temperature decreases the total amount of the tars and simultaneously reduces the contents of the oxygenated and alkyl-substituted poly

  4. Interfacial Reaction Dependent Performance of Hollow Carbon NanoSphere – Sulfur composite as a cathode for Li-S battery

    Directory of Open Access Journals (Sweden)

    Jianming eZheng


    Full Text Available Lithium-sulfur (Li-S battery is a promising energy storage system due to its high energy density, cost effectiveness and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li2S2/Li2S which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

  5. Local structure of alkalis in mixed-alkali borate glass to elucidate the origin of mixed-alkali effect

    Directory of Open Access Journals (Sweden)

    Yomei Tokuda


    Full Text Available We report the structural analysis of Na+ and Cs+ in sodium cesium borate crystals and glasses using 23Na and 133Cs magic-angle spinning nuclear magnetic resonance (MAS NMR spectroscopy. The composition dependence of NMR spectra of the borate was similar to that of the silicate: (1 the peak position of cesium borate crystals shifted to upfield for structures with larger Cs+ coordination numbers, (2 the MAS NMR spectra of xNa2O-yCs2O-3B2O3 (x = 0, 0.25, 0.5, 0.75, 1.0, x + y = 1 glass showed that the average coordination number (CN of both the alkali cations decreases with increasing Cs+/(Na+ + Cs+ ratio. However, the degree of decrement in borates is much smaller than that in silicates. We have considered that the small difference in CN is due to 4-coordinated B, because it is electrically compensated by the alkali metal ions resulting in the restriction of having various coordinations of O to alkali metal.

  6. Enhancement of reaction rates for catalytic benzaldehyde hydrogenation and sorbitol dehydration in water solvent by addition of carbon dioxide

    Indian Academy of Sciences (India)

    Masayuki Shirai; Osamu Sato; Norihito Hiyoshi; Aritomo Yamaguchi


    The effect of pressured carbon dioxide on heterogeneous hydrogenation of benzaldehyde and homogeneous dehydration of sorbitol in water solvent was studied. Initial hydrogenation rates of benzaldehyde over a charcoal-supported palladium catalyst in water at 313 K were enhanced by the addition of carbon dioxide. The initial rate increased with an increase in carbon dioxide pressure and became a maximum at 5 MPa. Dehydration of sorbitol proceeded in water phase at 500 K and initial dehydration rates were enhanced by addition of 30 MPa of carbon dioxide.

  7. Studies on interfacial behavior and wettability change phenomena by ionic and nonionic surfactants in presence of alkalis and salt for enhanced oil recovery (United States)

    Kumar, Sunil; Mandal, Ajay


    Surfactant flooding is one of the most promising method of enhanced oil recovery (EOR) used after the conventional water flooding. The addition of alkali improves the performance of surfactant flooding due to synergistic effect between alkali and surfactant on reduction of interfacial tension (IFT), wettability alteration and emulsification. In the present study the interfacial tension, contact angle, emulsification and emulsion properties of cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and polysorbate 80 (Tween 80) surfactants against crude oil have been investigated in presence of sodium chloride (NaCl) and alkalis viz. sodium hydroxide (NaOH), sodium carbonate (Na2CO3), ammonium hydroxide (NH4OH), sodium metaborate (SMB) and diethanolamine (DEA). All three surfactants significantly reduce the IFT values, which are further reduced to ultra-low value (∼10-4 mN/m) by addition of alkalis and salt. It has been found experimentally that alkali-surfactant systems change the wettability of an intermediate-wet quartz rock to water-wet. Emulsification of crude oil by surfactant and alkali has also been investigated in terms of the phase volume and stability of emulsion. A comparative FTIR analysis of crude oil and different emulsions were performed to investigate the interactions between crude oil and displacing water in presence of surfactant and alkali.


    The microwave reactions of InX3 with [Q]Y produce a series of tetrahaloindate(III)-based ionic liquids (ILs) with a general formula of [Q][InX3Y] (Q = imidazolium, phosphonium, ammonium, and pyridinium; X = Cl, Br, I; Y = Cl, Br). The reaction of CO2

  9. Improved hydrogen desorption from lithium hydrazide by alkali metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Liang, E-mail: [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Miyaoka, Hiroki [Institute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan)


    Highlights: •LiH can dramatically improve the hydrogen desorption properties of LiNHNH{sub 2}. •KH doping had positive effect in promoting the hydrogen desorption properties of LiNHNH{sub 2}–LiH mixture. •The reaction mechanism between LiNHNH{sub 2} and LiH was studied and discussed. -- Abstract: Lithium hydrazide (LiNHNH{sub 2}), which is a white solid with 8.0 mass% of theoretical hydrogen content, was synthesized from a reaction between anhydrous hydrazine and n-butyllithium in diethyl ether. The thermodynamic properties of this compound and its detailed decomposition pathways had been investigated in our previous work. However, a number of undesired gaseous products such as hydrazine (N{sub 2}H{sub 4}) and ammonia (NH{sub 3}) were generated during the thermal decomposition of LiNHNH{sub 2}. In this work, alkali metal hydride was used to suppress the impurities in the desorbed hydrogen and improved the hydrogen desorption properties. The reaction mechanism between LiNHNH{sub 2} and LiH was also studied and discussed in this paper.

  10. Removal of Retired Alkali Metal Test Systems

    Energy Technology Data Exchange (ETDEWEB)

    Brehm, W. F.; Church, W. R.; Biglin, J. W.


    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  11. Infrared spectra of FHF - in alkali halides (United States)

    Chunnilall, C. J.; Sherman, W. F.


    The bifluoride ion, FHF -, has been substitutionally isolated within single crystal samples of several different alkali halides. Infrared spectra of these crystals have been studied for sample temperatures down to 8K when half-bandwidths of less than 1 cm -1 have been observed. (Note that at room temperature ν 3 is observed to have a half-bandwidth of about 40 cm -1). The frequency shifts and half-bandwidth changes caused by cooling are considered together with the frequency shifts caused by pressures up to 10 k bar. The low temperature spectra clearly indicate that FHF - is a linear symmetrical ion when substitutionally isolated within alkali halides of either the NaCl or CsCl structure.

  12. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems. (United States)

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar


    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed.

  13. Porous Core-Shell Fe3C Embedded N-doped Carbon Nanofibers as an Effective Electrocatalysts for Oxygen Reduction Reaction. (United States)

    Ren, Guangyuan; Lu, Xianyong; Li, Yunan; Zhu, Ying; Dai, Liming; Jiang, Lei


    The development of nonprecious-metal-based electrocatalysts with high oxygen reduction reaction (ORR) activity, low cost, and good durability in both alkaline and acidic media is very important for application of full cells. Herein, we developed a facile and economical strategy to obtain porous core-shell Fe3C embedded nitrogen-doped carbon nanofibers (Fe3C@NCNF-X, where X denotes pyrolysis temperature) by electrospinning of polyvinylidene fluoride (PVDF) and FeCl3 mixture, chemical vapor phase polymerization of pyrrole, and followed by pyrolysis of composite nanofibers at high temperatures. Note that the FeCl3 and polypyrrole acts as precursor for Fe3C core and N-doped carbon shell, respectively. Moreover, PVDF not only plays a role as carbon resources, but also provides porous structures due to hydrogen fluoride exposure originated from thermal decomposition of PVDF. The resultant Fe3C@NCNF-X catalysts, particularly Fe3C@NCNF-900, showed efficient electrocatalytic performance for ORR in both alkaline and acidic solutions, which are attributed to the synergistic effect between Fe3C and N-doped carbon as catalytic active sites, and carbon shell protects Fe3C from leaching out. In addition, the Fe3C@NCNF-X catalyst displayed a better long-term stability, free from methanol crossover and CO-poisoning effects than those of Pt/C, which is of great significance for the design and development of advanced electrocatalysts based on nonprecious metals.

  14. Synergistically Enhanced Electrocatalytic Activity of Sandwich-like N-Doped Graphene/Carbon Nanosheets Decorated by Fe and S for Oxygen Reduction Reaction. (United States)

    Men, Bao; Sun, Yanzhi; Liu, Jia; Tang, Yang; Chen, Yongmei; Wan, Pingyu; Pan, Junqing


    Although N-doped graphene-based electrocatalysts have shown good performance for oxygen reduction reaction (ORR), they still suffer from the single-type active site in the as-prepared catalyst, limited accessible active surface area because of easy aggregation of graphene, and harsh condition for preparation process of graphene. Therefore, further developing a novel type of graphene-based electrocatalyst by a facile and environmentally benign method is highly anticipated. Herein, we first fabricate a sandwich-like graphene/carbon hybrid using graphene oxide (GO) and nontoxic starch. Then the graphene/carbon hybrid undergoes postprocessing with iron(III) chloride (FeCl3) and potassium sulfocyanide (KSCN) to acquire N-doped graphene/carbon nanosheets decorated by Fe and S. The resultant displays the features of interpenetrated three-dimensional hierarchical architecture composed of abundant sandwich-like graphene/carbon nanosheets and low graphene content in as-prepared sample. Remarkably, the obtained catalyst possesses favorable kinetic activity due to the unique structure and synergistic effect of N, S, and Fe on ORR, showing high onset potential, low Tafel slope, and nearly four-electron pathway. Meanwhile, the catalyst exhibits strong methanol tolerance and excellent long-term durability. In view of the multiple active sites, unique hierarchical structure, low graphene content, and outstanding electrochemical activity of the as-prepared sample, this work could broaden the thinking to develop more highly efficient graphene/carbon electrocatalysts for ORR in fuel cells.

  15. Sulfate Resistance of Alkali Activated Pozzolans


    Bondar, Dali


    The consequence of sulfate attack on geopolymer concrete, made from an alkali activated natural pozzolan (AANP) has been studied in this paper. Changes in the compressive strength, expansion and capillary water absorption of specimens have been investigated combined with phases determination by means of X-ray diffraction. At the end of present investigation which was to evaluate the performance of natural alumina silica based geopolymer concrete in sodium and magnesium sulfate solution, the l...

  16. Thermodynamic study of alkali metals release in pressurised fluidised-bed combustion and gasification of peat

    Energy Technology Data Exchange (ETDEWEB)

    Mojtahedi, W.; Backman, R.; Korhonen, M.


    A combined-cycle power generation system incorporating pressurised fluidised-bed combustion (PFBC) or gasification is considered a promising approach for electricity generation using solid fuels such as peat. In these systems, the high-pressure hot flue gas is expanded in a gas turbine. Peat contains sodium and potassium which are released in combustion and gasification. These are corrosive elements that can cause severe damage to the turbine blades if not suppressed. Multicomponent, multiphase equilibrium calculations were carried out for atmospheric and pressurised fluidised-bed operating conditions to determine the relative distribution of the two metals (Na and K) in the gas and condensed phases. Dependence of the alkali volatilisation on the operating temperature, pressure, the chlorine-content and the total alkali-content of the feedstock was studied. The results show that the alkali release in the vapour-phase could be much higher than acceptable to a gas turbine, particularly under gasification conditions. Hence the necessity to remove the volatilised alkali-metal compounds is more acute in gasification than in combustion. Both sodium and potassium are present as chlorides and to a lesser extent as hydroxides in the gas phase in both modes of operation (i.e. combustion and gasification). However, whereas under combustion conditions both metals seem to condense as sulphates (Na/sub 2/SO4 and K/sub 2/SO4), in gasification, chlorides and carbonates dominate in the condensed phase. The alkali-metals volatilisation shows strong dependence on the operating pressure of the system as well as on the chlorine-content of the feedstock. It decreases markedly with the former but increases sharply with the latter.

  17. Ion Pairing in Alkali Nitrate Electrolyte Solutions. (United States)

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin


    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities.

  18. Catalysis by alkali and alkaline-earth metal ions in nucleophilic attack of methoxide ion on crown ethers bearing an intra-annular acetoxy group

    NARCIS (Netherlands)

    Cacciapaglia, Roberta; Lucente, Silvia; Mandolini, Luigi; Doorn, van Arie R.; Reinhoudt, David N.; Verboom, Willem


    Rates of reaction of methoxide ion with crown ethers bearing an intra-annular acetoxy group are markedly enhanced by alkali and alkaline-earth metal bromides as a result of much stronger interactions of the metal ions with transition states than with reactants. Rates of reactions of methoxide ion w

  19. Solvothermal synthesis of LiFePO{sub 4} nanoplates with (010) plane and the uniform carbon coated on their surface by esterification reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Zhipeng [Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China); Shao, Guangjie, E-mail: [Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China); State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Wang, Xu [The Equipment Research Institute of the General Logistic Department of the CPLA, Beijing 100010 (China); Song, Jianjun; Wang, Guiling; Liu, Tingting [Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China)


    A facile solvothermal synthesis and esterification reaction combined with a high temperature calcination technique has been developed to prepare the uniform carbon coating LiFePO{sub 4} nanoplates. The carbon coating LiFePO{sub 4} nanoplates are investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), transmission electron microscope (TEM), galvanostatic intermittent titration technique (GITT) and galvanostatic charge–discharge test. A reasonable growth mechanism of LiFePO{sub 4} nanoplates is proposed on the basis of time dependent experimental results. The results show that each nanoplate is a LiFePO{sub 4} single crystal with the large (010) plane. According to Raman spectroscopy analysis, carbon is uniformly coated on the surface of LiFePO{sub 4} nanoplates. Electrochemical test results also indicate that the carbon coating LiFePO{sub 4} nanoplates exhibit a high reversible specific capacity of 144.8 mAh g{sup −1} at 0.5 C and 116.9 mAh g{sup −1} under lower discharging rate at −20 °C. - Highlights: • LiFePO{sub 4} nanoplates prepared by facile solvothermal synthesis expose large (010) plane. • The polyester network formed by the esterification reaction could entirely wrap LiFePO{sub 4}. • The polyester wrapped on the surface of LiFePO{sub 4} transformed into the uniform carbon layer after calcination. • LiFePO{sub 4}/C nanoplates have good high-rate and low-temperature performance.

  20. Emission Laws and Influence Factors of Greenhouse Gases in Saline-Alkali Paddy Fields

    Directory of Open Access Journals (Sweden)

    Jie Tang


    Full Text Available The study of greenhouse gas emissions has become a global focus, but few studies have considered saline-alkali paddy fields. Gas samples and saline-alkali soil samples were collected during the green, tillering, booting, heading and grain filling stages. The emission fluxes of CO2, CH4, and N2O as well as the pH, soil soluble salt, available nitrogen, and soil organic carbon contents were detected to reveal the greenhouse gas (GHG emission laws and influence factors in saline-alkali paddy fields. Overall, GHG emissions of paddy soil during the growing season increased, then decreased, and then increased again and peaked at booting stage. The emission fluxes of CO2 and CH4 were observed as having two peaks and a single peak, respectively. Both the total amount of GHG emission and its different components of CO2, CH4, and N2O increased with the increasing reclamation period of paddy fields. A positive correlation was found between the respective emission fluxes of CO2, CH4, and N2O and the available nitrogen and SOC, whereas a negative correlation was revealed between the fluxes of CO2, CH4, and N2O and soil pH and soil conductivity. The study is beneficial to assessing the impact of paddy reclamation on regional greenhouse gas emissions and is relevant to illustrating the mechanisms concerning the carbon cycle in paddy soils.

  1. The different poisoning behaviors of various alkali metal containing compounds on SCR catalyst (United States)

    Du, Xuesen; Yang, Guangpeng; Chen, Yanrong; Ran, Jingyu; Zhang, Li


    Alkali metals are poisonous to the metal oxide catalyst for NO removal. The chemical configuration of alkali containing substance and interacting temperature can affect the poisoning profile. A computational method based on Frontier Molecular Orbital analysis was proposed to determine the reacting behavior of various alkali-containing substances with SCR catalyst. The results reveal that the poisoning reactivities of various substances can be ranked as: E (MOH) > E (M2SO4) > E(MCl) > E(MNO3) > E(MHSO4). The experimental activity tests of the catalysts calcined at stepped temperatures show that NaOH can react with the catalyst below 200 °C. NaCl and NaNO3 start to react with the catalyst at a temperature between 300 and 400 °C. Unlike MOH, MCl and MNO3, which can produce volatile or decomposable species for the anions after reacting with the catalyst, M2SO4 and MHSO4 will leave both cations and anions on the catalyst surface. The sulfate ions left on the catalyst can generate active acid sites for NH3 adsorption. The experimental results also show that Na2SO4 and NaHSO4 will not lower the NO conversion. The after-reaction influences of various alkali metals were studied using theoretical and experimental methods. The theoretical results show that the acidity decreases with doping of alkali metal. Experiments show a consistent result that the NO conversion decreases as undoped >LiCl > NaCl > KCl.

  2. A Convenient Route to Higher Sugars by Two-Carbon Chain Elongation Using Wittig/Dihydroxylation Reactions

    DEFF Research Database (Denmark)

    Jørgensen, Morten; Iversen, Erik Høgh; Madsen, Robert


    The combination of a Wittig olefination and a dihydroxylation reaction constitutes a facile synthetic protocol for the transformation of unprotected carbohydrates into higher sugars. The Wittig reaction is carried out with tert-butyl or diphenylmethyl ester stabilized phosphoranes to give (E)-con...

  3. Role of Reaction and Factors of Carbon Nanotubes Growth in Chemical Vapour Decomposition Process Using Methane—A Highlight

    Directory of Open Access Journals (Sweden)

    Sivakumar VM


    This paper reviewed the synthesis of CNT by CVD especially focusing on methane CVD. Various parameters influencing the reaction and CNT growth were also discussed. A detailed review was made over the different types of CVD process, influence of metal, supports, metal-support interaction, effect of promoters, and reaction parameters role in CNTs growth.

  4. Catalytically active Au-O(OH)x-species stabilized by alkali ions on zeolites and mesoporous oxides. (United States)

    Yang, Ming; Li, Sha; Wang, Yuan; Herron, Jeffrey A; Xu, Ye; Allard, Lawrence F; Lee, Sungsik; Huang, Jun; Mavrikakis, Manos; Flytzani-Stephanopoulos, Maria


    We report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH)x-(Na or K) ensembles. This single-site gold species is active for the low-temperature (alkali ions and establishing an active site on various supports. The intrinsic activity of the single-site gold species is the same on irreducible supports as on reducible ceria, iron oxide, and titania supports, apparently all sharing a common, similarly structured gold active site. This finding paves the way for using earth-abundant supports to disperse and stabilize precious metal atoms with alkali additives for the WGS and potentially other fuel-processing reactions.

  5. The influence of chlorine on the fate and activity of alkali metals during the gasification of wood

    Energy Technology Data Exchange (ETDEWEB)

    Struis, R.; Scala, C. von; Schuler, A.; Stucki, S. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    Chlorine clearly inhibits the CO{sub 2}-gasification reaction of charcoal at 800{sup o}C. From this and other observations the picture emerges that the reduction in the gasification reactivity of the charcoal is intimately related to the deactivation of the catalytically active alkali metals residing in the wood due to the formation of the chloride salt. It is argued that the heavy metal chlorides will likely transfer the chlorine to the indigenous alkali metals during the pyrolysis stage of the wood. The fate of the thus formed alkali metal chlorides can then be either their removal from the sample (evaporation), or, when present at the gasification stage, re-activation (i.e., de-chlorination) under our gasification conditions. (author) 3 figs., 4 refs.

  6. Structural and surface coverage effects on CO oxidation reaction over carbon-supported Pt nanoparticles studied by quadrupole mass spectrometry and diffuse reflectance FTIR spectroscopy. (United States)

    Cheah, Seng Kian; Bernardet, Véronique P; Franco, Alejandro A; Lemaire, Olivier; Gelin, Patrick


    The CO oxidation reaction on carbon-supported Pt nanoparticles (average size of 2.8 to 7.7 nm) was studied under flowing conditions at atmospheric pressure and temperatures between 300 and 353 K by coupling quadrupole mass spectrometry (QMS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The Pt loading was varied between 20 and 60 wt%. Gases diluted in He (0.5 mol%) were used together with Ar as a tracer. Reactions with CO and O2 introduced separately onto the samples were studied by QMS, applying successive step changes of the reaction mixtures. Variations in the rate of the reactions were observed and correlated with changes of the calculated coverage of the Pt surface by CO and/or O adspecies at varying steps of the experiment. The transient reaction of CO(g) with adsorbed O (Oad) was fast and mass transport-limited while that of O2(g) with adsorbed CO (COad) was sluggish. Following the same experimental procedures, FTIR spectra of adsorbed CO after varying steps were recorded, confirming the variations of COad and Oad as determined by QMS and indicating changes in the CO distribution over varying types of Pt surface sites. The influence of the adlayer composition (co-adsorption of COad and Oad), the particle size/structure and some possible surface reconstruction effects on the CO oxidation rate were evidenced and discussed. The structure of the Pt nanoparticles supported on carbon appears as an important factor for the efficiency of the so-called O2 bleeding as a CO mitigation strategy in polymer electrolyte membrane fuel cells.

  7. Alkali-activated binders/geopolymer and an application to environmental engineering

    Directory of Open Access Journals (Sweden)

    Nida Chaimoon


    Full Text Available For environmental reason, new binders that can be used as Portland cement replacement materials are being needed. Recently, alkali-activated binders (AAB and geopolymer have found increasing interest. As several research reports have showed that the two new binders are likely to have high potential to be developed and become an alternative to OPC. However, confusion in the classification of both binders is still there. This paper reviews knowledge about AAB and geopolymer including historical background, reaction mechanisms and reaction products. The similarities and differences of both binders are discussed. The application to environmental engineering on hazardous waste management using stabilization/solidification is also described.

  8. Hydrothermal synthesis of mixed rare earth-alkali metal or ammonium fluorides

    Institute of Scientific and Technical Information of China (English)

    由芳田; 黄世华; 时秋峰


    The recent results on hydrothermal synthesis of mixed rare earth-alkali or ammonium fluorides were presented. The initial ratios of the starting materials, pH value and reaction temperature were the critical factors for obtaining the single-phase product. Four main types of complex rare earth fluorides, AREF4, A2REF5, ARE2F7 and ARE3F10 (A=Na+, K+, Rb+, NH4+), appeared in the primary hydrothermal reactions. The correlation between cation sizes and the formation of mixed rare earth fluorides under mild hydro...

  9. Effect of Reaction Temperature in the Selective Synthesis of Single Wall Carbon Nanotubes (SWNT) on a Bimetallic CoCr-MCM-41 Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Zoican Loebick, C.; Abanulo, D; Majewska, M; Haller, G; Pfefferle, L


    Synthesis of single wall carbon nanotubes (SWNT) on a CoCr-MCM-41 bimetallic catalyst by CO disproportionation has been carried out at five different temperatures between 500 and 900 C. A series of methods have been employed for a comprehensive assessment effect of temperature on the size-controllability of the catalyst particles and the morphology of the resultant SWNT. By extended fine structure X-ray absorption, thermogravimetric analysis, resonance Raman spectroscopy, photoluminescence excitation (PLE) mapping and transmission electron microscopy we found an optimal synthesis temperature window between 600 and 800 C. In this window, modifying the reaction temperature leads to significant changes in the SWNT yield, diameter and chirality distribution. Decrease in reaction temperature favored the selective synthesis of very small diameter carbon nanotubes (as low as 0.6 nm). Chirality dependence of SWNT on temperature has been measured by PLE. A progressive suppression of larger diameter SWNT identities in the measured SWNT population was noted when reaction temperature decreased. In the measured PL maps, two near armchair structures (6,5) and (7,3) were dominant at 600 and 700 C.

  10. Internal Active Thermal Control System (IATCS) Sodium Bicarbonate/Carbonate Buffer in an Open Aqueous Carbon Dioxide System and Corollary Electrochemical/Chemical Reactions Relative to System pH Changes (United States)

    Stegman, Thomas W.; Wilson, Mark E.; Glasscock, Brad; Holt, Mike


    The International Space Station (ISS) Internal Active Thermal Control System (IATCS) experienced a number of chemical changes driven by system absorption of CO2 which altered the coolant’s pH. The natural effects of the decrease in pH from approximately 9.2 to less than 8.4 had immediate consequences on system corrosion rates and corrosion product interactions with specified coolant constituents. The alkalinity of the system was increased through the development and implementation of a carbonate/bicarbonate buffer that would increase coolant pH to 9.0 – 10.0 and maintain pH above 9.0 in the presence of ISS cabin concentrations of CO2 up to twenty times higher than ground concentrations. This paper defines how a carbonate/bicarbonate buffer works in an open carbon dioxide system and summarizes the analyses performed on the buffer for safe and effective application in the on-orbit system. The importance of the relationship between the cabin environment and the IATCS is demonstrated as the dominant factor in understanding the system chemistry and pH trends before and after addition of the carbonate/bicarbonate buffer. The paper also documents the corollary electrochemical and chemical reactions the system has experienced and the rationale for remediation of these effects with the addition of the carbonate/bicarbonate buffer.

  11. Alkali activated fly ash binders. A comparative study between sodium and potassium activators

    Directory of Open Access Journals (Sweden)

    Criado, M.


    Full Text Available This paper shows the effect of the nature of some alkaline activators in the microstructural development of thermal-alkali activated f/y ash systems. The alkaline compounds employed in this investigation were: NaOH, KOH, Na2C03, K2C03, sodium silicate and potassium silicate. Results confirm that the main reaction product of the activation process (throughout the studied systems is the amorphous alkaline aluminosilicate gel with a three-dimensional structure already observed in earlier research. It has been proved that the type of anion and cation involved in the activation reaction of the ashes not only affects the microstructural development of the systems but the Si/Al ratio of that prezeolitic gel too. For example, in the presence of soluble silicate ions the content of Si in the final structure is notably increased (Si/Al =2.7-3.0, however carbonate ions play a different role since the formation of Sodium or Potassium carbonate/bicarbonate acidifies the system and consequently the reaction rate is considerably slowed. Finally it is evident that; when all experimental conditions are equal, sodium has a greater capacity than potassium to accelerate the setting and hardening reactions of fly ash and also to stimulate the growth of certain zeolitic crystals (reaction by-products. In general it can be affirmed that OH- ion acts as a reaction catalyst; and the alkaline metal (M+ acts as a structure-forming element.Este trabajo muestra el efecto de la naturaleza del activador alcalino en el desarrollo microestructural de sistemas de ceniza volante, activados térmica y alcalinamente. Los componentes alcalinos empleados en esta investigación fueron: NaOH, KOH, Na2C03, K2C03, silicato sódico y silicato potásico. Los resultados obtenidos confirman que el principal producto de reacción del proceso de activación (a través de los sistemas estudiados es un gel de aluminosilicato alcalino amorfo con estructura tridimensional ya observada en trabajos

  12. Thermalization of different alkali and alkali-earth elements at the TRI{mu}P facility

    Energy Technology Data Exchange (ETDEWEB)

    Shidling, P.D., E-mail: P.Shidling@rug.n [Kernfysisch Versneller Instituut, University of Groningen, Zernikelaan 25, 9747 AA Groningen (Netherlands); Giri, G.S.; Hoek, D.J. van der; Jungmann, K.; Kruithof, W.L.; Onderwater, C.J.G.; Santra, B.; Sohani, M.; Versolato, O.O.; Willmann, L.; Wilschut, H.W. [Kernfysisch Versneller Instituut, University of Groningen, Zernikelaan 25, 9747 AA Groningen (Netherlands)


    Radioactive isotopes produced by the in-flight method are converted into low-energy ions with a thermal ionizer (TI) ion catcher, the operation of which is based on a hot cavity ion source. The extraction efficiency of the TI for different alkali and alkali-earth elements has been studied and compared to a model based on diffusion only. The model describes the stationary limit, i.e. the extraction efficiency, as well as the dynamic response of the TI output when the primary beam is switched on and off.

  13. Hydrogen Adsorption by Alkali Metal Graphite Intercalation Compounds (United States)

    Purewal, Justin

    Adsorption occurs whenever a solid surface is exposed to a gas or liquid, and is characterized by an increase in fluid density near the interface. Adsorbents have drawn attention in the current effort to engineer materials that store hydrogen at high densities within moderate temperature and pressure regimes. Carbon adsorbents are a logical choice as a storage material due to their low costs and large surface areas. Unfortunately, carbon adsorbents suffer from a low binding enthalpy for H2 (about 5 kJ mol-1), well below the 15 to 18 kJ mol-1) that is considered optimal for hydrogen storage systems. Binding interactions can be increased by the following methods: (1) adjusting the graphite interplanar separation with a pillared structure, and (2) introducing dopant species that interact with H2 molecules by strong electrostatic forces. Graphite intercalation compounds are a class of materials that contain both pillared structures and chemical dopants, making them an excellent model system for studying the fundamentals of hydrogen adsorption in nanostructured carbons. Pressure-composition-temperature diagrams of the MC24(H 2)x graphite intercalation compounds were measured for M = (K, Rb, Cs). Adsorption enthalpies were measured as a function of H2 concentration. Notably, CsC24 had an average adsorption enthalpy of 14.9 kJ mol-1), nearly three times larger than that of pristine graphite. The adsorption enthalpies were found to be positively correlated with the alkali metal size. Adsorption capacities were negatively correlated with the size of the alkali metal. The rate of adsorption is reduced at large H2 compositions, due to the effects of site-blocking and correlation on the H2 diffusion. The strong binding interaction and pronounced molecular-sieving behavior of KC24 is likely to obstruct the translational diffusion of adsorbed H2 molecules. In this work, the diffusion of H2 adsorbed in KC24 was studied by quasielastic neutron scattering measurements and molecular

  14. Insights into gas-phase reaction mechanisms of small carbon radicals using isomer-resolved product detection. (United States)

    Trevitt, Adam J; Goulay, Fabien


    For reactive gas-phase environments, including combustion, extraterrestrials atmospheres and our Earth's atmosphere, the availability of quality chemical data is essential for predictive chemical models. These data include reaction rate coefficients and product branching fractions. This perspective overviews recent isomer-resolved production detection experiments for reactions of two of the most reactive gas phase radicals, the CN and CH radicals, with a suite of small hydrocarbons. A particular focus is given to flow-tube experiments using synchrotron photoionization mass spectrometry. Coupled with computational studies and other experiment techniques, flow tube isomer-resolved product detection have provided significant mechanistic details of these radical + neutral reactions with some general patterns emerging.

  15. An alternative picture of alkali-metal-mediated metallation: cleave and capture chemistry. (United States)

    Mulvey, Robert E


    This perspective article takes an alternative look at alkali-metal-mediated chemistry (exchange of a relatively inert C-H bond for a more reactive C-metal bond by a multicomponent reagent usually containing an alkali metal and a less electropositive metal such as magnesium or zinc). It pictures that the cleavage of selected C-H bonds can be accompanied by the capturing of the generated anion by the multi (Lewis acid)-(Lewis base) character of the residue of the bimetallic base. In this way small atoms or molecules (hydrides, oxygen-based anions) as well as sensitive organic anions (of substituted aromatic compounds, ethers or alkenes) can be captured. Cleave and capture reactions which occur in special positions on the organic substrate are also included.

  16. Alkali ion migration between stacked glass plates by corona discharge treatment (United States)

    Kawaguchi, Keiga; Suzuki, Toshio; Ikeda, Hiroshi; Sakai, Daisuke; Funatsu, Shiro; Uraji, Keiichiro; Yamamoto, Kiyoshi; Harada, Kenji; Nishii, Junji


    Corona discharge reflects the spatial migration of alkali ions over a gap between two glass plates. This study examined stacked glass plates containing different alkali ions treated with the corona discharge plasma generated by applied voltage of 4.5 kV at 200 °C. Protons generated at the anode electrode penetrate into the potassium-ion-containing upper glass plate, which is located 5 mm below the anode electrode. Potassium ions intruded into the lower glass plate containing sodium ions placed on the cathode electrode, even over a 1 mm gap separating the plates. Finally, the sodium ion discharged on the cathode electrode. The hydrogen atmosphere was effective at inhibiting the potassium ion reaction with ambient gases during the spatial migration between the two glass plates.

  17. Alkali Induced Morphology and Property Improvements of TiO2 by Hydrothermal Treatment

    Institute of Scientific and Technical Information of China (English)

    HE Qiong; WEN Xianming; MA Peihua; DENG Xiaochuan


    Alkali induced morphology and property improvements of TiO2 by hydrothermal reaction were investigated.The products were characterized by SEM,TEM,XRD,TG,EDX,FT-IR and DRS.The results indicate that,with the phase transformation from anatase to rutile,the morphologies changed from high aggregated particles to nanofibers with the diameter of about 100 nm and the length up to several tens of micrometers,meanwhile the process is controllable by manipulating the nature of the alkali,alkalinity and hydrothermal temperature.DRS analysis shows the property improvement of the nanofibers in the UV-Vis light absorption compared with the raw materials,implying the products have potential application in photocatalysis.

  18. Mechanistic investigation and modelling of anode reaction in the molten carbonate fuel cell; Mechanistische Untersuchung und Modellierung der Anodenreaktion in der Karbonat-Brennstoffzelle

    Energy Technology Data Exchange (ETDEWEB)

    Schuster, Markus Roman


    Considering distributed energy generation, molten carbonate fuel cells (MCFCs) have best prospects to fulfil the demands of the highly competing energy market. To establish MCFC technology in the market, various requirements need to be met. These are on the one hand the reduction of the specific costs per kW and the simultaneous increase in efficiency of the MCFCs. On the other hand, an extended lifetime of MCFC stacks in general and especially when biofuels are used is required. Detailed knowledge of electrodes' reaction mechanisms is essential for successful technical improvements or cost reduction measures. In this thesis, the complex anodic reaction mechanism in the molten carbonate fuel cell is studied in detail, with the objective to develop a fundamental understanding of the physical and electrochemical processes taking place at the anode, and to identify the factors influencing the performance of fuel cell stacks. These include a detailed study of the simultaneously performed oxidation reactions of hydrogen and carbon monoxide and its kinetic parameters, the detailed analysis of mass transport, adsorption and charge transfer and the observation of degradation phenomena, which have a declining effect on cell performance and lifetime. In order to gain this knowledge, several testing facilities have been used: anode half-cells and single cells. Electrochemical impedance spectroscopy (EIS) has been applied as analyzing tool for physical and electrochemical phenomena, whose results have been integrated in the development of an equivalent circuit. Linking the elements of the equivalent circuit with physical process parameters has been done by using a numerical model for the MCFC-anode. The impedance measurements of the MCFC anodes result in four characteristic resistances: ohmic resistance, high-frequency resistance, low-frequency resistance and cumulative resistance. The strongly temperature dependent high-frequency resistance is influenced by the electrode

  19. Analysis of phosphate-accumulating organisms cultivated under different carbon sources with polymerase chain reaction-denaturing gradient gel electrophoresis assay

    Institute of Scientific and Technical Information of China (English)

    YU Shui-li; LIU Ya-nan; JING Guo-lin; ZHAO Bing-jie; GUO Si-yuan


    To investigate the microbial communities of microorganisms cultivated under different carbon sources, three sequencing batch reactors were operated. They were supplied with sewage, glucose and sodium acetate as carbon sources respectively and showed high phosphorus removal performance. The results of denaturing gradient gel electrophoresis(DGGE) of polymerase chain reaction-amplified (PCR) 16S rDNA fragments demonstrated that β-protebacteria, Actinomyces sp. and γ-protebacteria only exited in 1 # reactor. The microbiological diversity of 1 # reactor exceeded the other two reactors. Flavobacterium, Bacillales, Actinomyces, Actinobacteridae and uncultured bacteria(AF527584, AF502204, AY592749, AB076862, AJ619051, AF495454 and AY133070) could be detected in the biological phosphorus removal reactors.

  20. Foaming behaviour equation for foam originating from carbonate decomposition reaction in Na{sub 2}B{sub 4}O{sub 7} melt

    Energy Technology Data Exchange (ETDEWEB)

    Wu Keng; Zhang Erhua; Chen Chunyuan; Chu Shaojun; Li Hongmin [Beijing Univ. of Science and Technology, BJ (China)


    The foaming behaviour equations were given for the foam originating from carbonate decomposition in the Na{sub 2}B{sub 4}O{sub 7} melt. The foam height was measured during the foaming phenomenon under different conditions in the laboratory. The formation and rupture coefficients (K and k) in the foam behaviour equation were determined by means of regression of the experimental data. The parameters such as temperature, size, crystal types of carbonate, the composition of melt and so on have an influence on the foaming phenomenon. With K and k the formation and rupture processes could be described quantitatively. The relationship between the foam height and the foaming phenomenon duration could be expressed quantitatively. This method can be used to describe quantitatively the foaming phenomenon originating from reaction in the melt. (orig.)