Effect of acetonitrile on the solubility of carbon dioxide in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide

The effect of the addition of acetonitrile on the solubility of carbon dioxide in an ionic liquid, the 1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)amide, [C(2)mim][NTf2], was studied experimentally at pressures close to atmospheric and as a function of temperature between 290 and 335 K. It was observed that the solubility of carbon dioxide decreases linearly with the mole fraction of acetonitrile from a value of 2.6 x 10(-2) in the pure ionic liquid at 303 K to a mole fraction of 1.3 x 10(-2) in the mixture [C(2)mim][NTf2] + CH3CN with x(CH3CN) = 0.77 at the same temperature. The gas solubility decreases with temperature, and the thermodynamic properties of solvation could be calculated. The vapor pressures of the [ C2mim][ NTf2] + CH3CN mixtures were measured in the same temperature range, and strong negative deviations from Raoult's law were obtained: up to 36% for a mixture with x(CH3CN) = 0.46 at 334 K. Negative excess molar volumes of approximately -1 cm(3) mol(-1) at equimolar composition could also be calculated from density measurements of the pure components and of the mixtures. These observations are confirmed by neutron diffraction studies and are compatible with the existence of strong ion-dipole interactions in the mixed liquid solvent.

Ultrafast Melting of Carbon Induced by Intense Proton Beams

Laser-produced proton beams have been used to achieve ultrafast volumetric heating of carbon samples at solid density. The isochoric melting of carbon was probed by a scattering of x rays from a secondary laser-produced plasma. From the scattering signal, we have deduced the fraction of the material that was melted by the inhomogeneous heating. The results are compared to different theoretical approaches for the equation of state which suggests modifications from standard models.

Effect of activated carbon xerogel pore size on the capacitance performance of ionic liquid electrolytes

The use of ionic liquid (IL) electrolytes promises to improve the energy density of electrochemical capacitors (ECs) by allowing for operation at higher voltages. Several studies have also shown that the pore size distribution of materials used to produce electrodes is an important factor in determining EC performance. In this research the capacitative, energy and power performance of ILs 1-ethyl-3- methylimidazolium tetrafluoroborate (EMImBF4), 1-ethyl-3-methylimidazolium dicyanamide (EMImN(CN)2), 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide (DMPImTFSI), and 1-butyl-3-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (BMPyT(F5Et)PF3) were studied and compared with the commercially utilised organic electrolyte 1M tetraethylammonium tetrafluoroborate solution in anhydrous propylene carbonate (Et4NBF4–PC 1 M). To assess the effect of pore size on IL performance, controlled porosity carbons were produced from phenolic resins activated in CO2. The carbon samples were characterised by nitrogen adsorption– desorption at 77 K and the relevant electrochemical behaviour was characterised by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The best capacitance performance was obtained for the activated carbon xerogel with average pore diameter 3.5 nm, whereas the optimum rate performance was obtained for the activated carbon xerogel with average pore diameter 6 nm. When combined in an EC with IL electrolyte EMImBF4 a specific capacitance of 210 F g1 was obtained for activated carbon sample with average pore diameter 3.5 nm at an operating voltage of 3 V. The activated carbon sample with average pore diameter 6 nm allowed for maximum capacitance retention of approximately 70% at 64 mA cm2.

Thermophysical properties, low pressure solubilities and thermodynamics of solvation of carbon dioxide and hydrogen in two ionic liquids based on the alkylsulfate anion

Densities and viscosities of the ionic liquid 1-butyl-3-methylimidazolium octylsulfate, [C4C1Im][C8SO4] were measured as a function of temperature between 313 K and 395 K. Solubilities of hydrogen and carbon dioxide were determined, between 283 K and 343 K, and at pressures close to atmospheric in [C4C1Im][C 8SO4] and in another ionic liquid based on the alkylsulfate anion-1-ethyl-3-methylimidazolium ethylsulfate, [C 2C1Im][C2SO4]. Density and viscosity were measured using a vibrating tube densimeter from Anton Paar and a rheometer from Rheometrics Scientific with accuracies of 10-3 g cm -3 and 1%, respectively. Solubilities were obtained using an isochoric saturation technique and, from the variation of solubility with temperature, the partial molar thermodynamic functions of solvation, such as the standard Gibbs energy, the enthalpy, and the entropy, are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is better than ±1%. © The Royal Society of Chemistry.

Density Functional study of the photoactive yellow protein's chromophore

We have investigated the structural and electronic properties of p-coumaric acid, the chromophore of the photoactive yellow protein (PYP), by means of first-principles molecular dynamics based on density functional theory (DFT). We have studied the chromophore both in the vacuum and in an extended model which includes the nearest residues in the binding pocket of PYP, as derived from crystallographic data. We have characterized the ground state of the isolated chromophore in its protonated and deprotonated forms and computed the energy barrier involved in the trans to cis isomerization process around the carbon-carbon double bond. A comparison of the optimized structures of the chromophore in the vacuum and in the extended protein model, both in the trans (ground state of PYP in the dark) and cis (first light-activated intermediate) configuration, shows how the protein environment affects the chromophore in the first step of the photocycle. Our model gives an energy storage of 25 kcal/mol associated with the trans-to-cia photoisomerization. Finally, we have elucidated the nature of the electronic excitation relevant for the photochemistry of PYP by means of time-dependent DFT calculations.

Charge equilibrium of a laser-generated carbon-ion beam in warm dense matter

Using ion carbon beams generated by high intensity short pulse lasers we perform measurements of single shot mean charge equilibration in cold or isochorically heated solid density aluminum matter. We demonstrate that plasma effects in such matter heated up to 1 eV do not significantly impact the equilibration of carbon ions with energies 0.045-0.5 MeV/nucleon. Furthermore, these measurements allow for a first evaluation of semiempirical formulas or ab initio models that are being used to predict the mean of the equilibrium charge state distribution for light ions passing through warm dense matter.

Reactive dye adsorption onto a novel mesoporous carbon

A new mesoporous carbon (MCSG60) was developed using an inexpensive commercial mesoporous silica gel as a template and sucrose as the carbon source. The surface area, porosity and density of the carbon were determined. The material possesses a high specific surface area and pore volume accessible for most typical aqueous pollutants. The adsorbent material was tested in a batch dye adsorption system. The behaviour of three reactive dyes adsorbed onto MCSG60 was evaluated (Naphthol Blue Black, NBB; Reactive Black 5, RB5; and Remazol Brilliant Blue R, RBBR). The maximum adsorption capacities obtained for the dyes were: 270. mg/g for NBB; 270. mg/g for RB5; and 280. mg/g for RBBR. Kinetic studies indicated that the adsorption process onto the mesoporous carbon was rapid and that equilibrium was reached in less than 1. h for all the dye systems investigated. Further batch experiments showed MCSG60 successfully adsorbed the dyes over a wide pH range and at low adsorbate concentration. The adsorption potential of MCSG60 for dye removal was further evaluated using a fixed-bed adsorption column. © 2013 Elsevier B.V.

A Lead-Free and High-Energy Density Ceramic for Energy Storage Applications

In this work, we demonstrate a very high-energy density and high-temperature stability capacitor based on SrTiO3-substituted BiFeO3 thin films. An energy density of 18.6 J/cm3 at 972 kV/cm is reported. The temperature coefficient of capacitance (TCC) was below 11% from room temperature up to 200°C. These results are of practical importance, because it puts forward a promising novel and environmentally friendly, lead-free material, for high-temperature applications in power electronics up to 200°C. Applications include capacitors for low carbon vehicles, renewable energy technologies, integrated circuits, and for the high-temperature aerospace sector. © 2013 Crown copyright

Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

Selective Hydrogenation of Acetylene over Pd-Boron Catalysts: A Density Functional Theory Study

Boron-modified Pd catalysts have shown excellent performance for the selective hydrogenation of alkynes experimentally. In the current work, we investigated the hydrogenation of acetylene on boron-modified Pd(111) and Pd(211) surfaces, utilizing density functional theory calculations. The activity of acetylene hydrogenation has been studied by estimating the effective barrier of the whole process. The selectivity of ethylene formation is investigated from a comparison between the desorption and the hydrogenation of ethylene as well as comparison between the ethylene and the 1,3-butadiene formation. Formation of subsurface carbon and hydrogen on both boron-modified Pd(111) and Pd(211) surfaces has also been evaluated, since these have been reported to affect both the activity and the selectivity of acetylene hydrogenation to produce ethylene on Pd surfaces. Our results provide some important insights into the Pd B catalysts for selective hydrogenation of acetylene and also for more complex hydrogenation systems, such as stereoselective hydrogenation of longer chain alkynes and selective hydrogenation of vegetable oil.

Generation of high-energy-density ion bunches by ultraintense laser-cone-target interaction

A scheme in which carbon ion bunches are accelerated to a high energy and density by a laser pulse (∼10 W/cm) irradiating cone targets is proposed and investigated using particle-in-cell simulations. The laser pulse is focused by the cone and drives forward an ultrathin foil located at the cone's tip. In the course of the work, best results were obtained employing target configurations combining a low-Z cone with a multispecies foil transversely shaped to match the laser intensity profile. © 2014 AIP Publishing LLC.

The impacts of replacing air bubbles with microspheres for the clarification of algae from low cell-density culture

Dissolved Air Flotation (DAF) is a well-known coagulation-flotation system applied at large scale for microalgae harvesting. Compared to conventional harvesting technologies DAF allows high cell recovery at lower energy demand. By replacing microbubbles with microspheres, the innovative Ballasted Dissolved Air Flotation (BDAF) technique has been reported to achieve the same algae cell removal efficiency, while saving up to 80% of the energy required for the conventional DAF unit. Using three different algae cultures (Scenedesmus obliquus, Chlorella vulgaris and Arthrospira maxima), the present work investigated the practical, economic and environmental advantages of the BDAF system compared to the DAF system. 99% cells separation was achieved with both systems, nevertheless, the BDAF technology allowed up to 95% coagulant reduction depending on the algae species and the pH conditions adopted. In terms of floc structure and strength, the inclusion of microspheres in the algae floc generated a looser aggregate, showing a more compact structure within single cell alga, than large and filamentous cells. Overall, BDAF appeared to be a more reliable and sustainable harvesting system than DAF, as it allowed equal cells recovery reducing energy inputs, coagulant demand and carbon emissions. © 2014 Elsevier Ltd.

Viscosity and Carbon Dioxide Solubility for LiPF6, LiTFSI, and LiFAP in Alkyl Carbonates: Lithium Salt Nature and Concentration Effect

Density Functional Study on Reaction Activity of Steam Decomposition Products Adsorbed on Carbonaceous Surface

A systematic theoretical study on the adsorption of steam and its thermal decomposition products on carbon both zigzag and armchair surface was performed to provide molecular-level understanding of the reaction activity of all these reactants in biomass steam gasification process. All the calculations were carried out using density functional theory (DFT) at the B3LYP/6-31+g(d,p) level. The structures of carbonaceous surfaces, all reactants and surface complexes were optimized and characterized. Based on the value of adsorption heat been obtained from the calculation, the activity of all reactants can be ordered as: O > O2 >H2 >H >OH >H2O for both zigzag and armchair surface, and the adsorption style is physisorption to water molecule and chemisorption to the other dissociated components.

Investigation of the solid-liquid phase transition of carbon at 150 GPa with spectrally resolved X-ray scattering

We have resolved the solid-liquid phase transition of carbon at pressures around 150GPa. High-pressure samples of different temperatures were created by laser-driven shock compression of graphite and varying the initial density from 1.30g/cm³ to 2.25g/cm³. In this way, temperatures from 5700K to 14,500K could be achieved for relatively constant pressure according to hydrodynamic simulations. From measuring the elastic X-ray scattering intensity of vanadium K-alpha radiation at 4.95keVat a scattering angle of 126°, which is very sensitive to the solid-liquid transition, we can determine whether the sample had transitioned to the fluid phase. We find that samples of initial density 1.3g/cm³ and 1.85g/cm³ are liquid in the compressed states, whereas samples close to the ideal graphite crystal density of 2.25g/cm³ remain solid, probably in a diamond-like state.