Photoluminescence of fluoroacrylate polymers impregnated with Eu(bta)<Subscript>3</Subscript> using supercritical CO<Subscript>2</Subscript>

Optical properties (photoluminescence and absorption) of Eu(bta)₃(B) _n (B = H₂O or 1,10-phenanthroline) polycrystalline powders and fluoroacrylate polymers (FAPs) impregnated with these compounds using supercritical CO₂ (SC CO₂) were investigated. It was established that impregnation of Eu(bta)₃phen into the FAPs using an SC CO₂ solution was difficult to achieve. The type of B (ancillary ligand) and the polymer matrix were shown to influence the temperature quenching of photoluminescence of Eu³⁺ ions in the range 25–100°C. A comparative analysis of quantum yields (λ_ex = 300 and 380 nm) and photoluminescence decay times (λ_ex = 337.1 nm) for Eu(bta)₃B _n and for Eu(bta)₃B _n -doped FAPs was performed.     

Effect of treatment in supercritical CO<Subscript>2</Subscript> on the composition and structure of tealeaf and cellulose

The influence of the pretreatment procedures with supercritical CO₂ (SC-CO₂) on the elemental composition of tealeaf is studied. Fourier-transform infrared absorption spectroscopy is used to examine the effect of SC-CO₂ on the structure of Chinese green tea and cellulose.     

Impregnation of Polycarbonate by Paramagnetic Probe 2,2,6,6-Tetramethyl-4-Hydroxy-Piperidine-1-Oxyl (TEMPOL) in Supercritical CO<Subscript>2</Subscript>

The aim of the research was to test the advantages of spin probe electron paramagnetic resonance approach in studying polymers impregnation with organic molecules in supercritical CO₂ (scCO₂) The impregnation of bisphenol A polycarbonate with the spin probe TEMPOL was carried out at 307–343 K and 11.6–35 MPa. The mean and local concentrations of the spin probe in the polymer were evaluated. An increase in temperature and pressure resulted in a more even distribution of the dopant in the polymer matrix. It was observed that, at 307 K and 19.6 MPa, the spin probe was located only near the surface of the sample. Local mobility of the spin probe molecules was found to be similar in polycarbonate films impregnated in scCO₂ and cast from dichloroethane solution. It was shown that changes in the structure of the surface and bulk of the polymer detected by the atomic force and optical polarization microscopy are not directly related with the distribution of the dopant molecules and their average content in the polymer.     

Dual-functional materials for interface modifications in solid-state dye-sensitised TiO<Subscript>2</Subscript> solar cells

The concept of solid-state dye-sensitised TiO₂ solar cells with an organic semiconductor as hole-transport medium is studied in detail by examining the dye–hole conductor interface. The facile transfer of holes from Ru-dye core to the hole conductor requires suitable interface modifiers which have the function of dye and hole transport moiety, but with exactly positioned anchor groups and antenna functions. The synthesis and characterisation of such novel low molecular weight multifunctional molecules carrying dye units and triphenylamine moieties are presented and their influence as interface modifiers is studied. This interface modification results in doubling the external quantum efficiency of current conversion via improved charge transfer at the dye–hole conductor interface. Moreover, the recombination processes at this interface are drastically suppressed, which leads to higher open-circuit voltage and consequently higher power-conversion efficiency. The concept is also extended to polymers to obtain dye-centred polymeric hole conductors which carry a single Ru-dye unit in the middle of the poly(vinyltriphenylamine) chain that acts as hole-conductor polymer. The polymerisation was carried out by atom-transfer radical polymerisation of 4-bromostyrene followed by polymer amination and finally metallation with Ru-bis(bipyridyl) precursors . PACS 81.07.Bc; 81.05.Lg; 81.16.Dn; 81.20.Fw; 84.60.Jt     

Molecular Simulation of H<Subscript>2</Subscript>O,CO<Subscript>2</Subscript>, and CH<Subscript>4</Subscript> Adsorption in Coal Micropores

Based on the chemical model of coal, slit micropores with different pore sizes are established and structures are optimized in the software of materials studio. As the temperature rises, absolute adsorption capacities of H₂O are slightly affected, while absolute adsorption capacities of CO₂ and CH₄ gradually decrease. As the fugacity rises, excess adsorption curves of CO₂ experience increase-decrease-gentle three stages, while the curves of CH₄ gradually decrease. With the increase of pore size, adsorption capacities of H₂O increase, while adsorption capacities of CO₂ and CH₄ gradually decrease. H₂O firstly adsorbs on the oxygen-containing functional group, so the walls of pore are the preferential area for H₂O, while CO₂ and CH₄ choose to adsorb on–C–C–, therefore the walls are the primary area for CO₂ and CH₄. Strong potential in micropores and hydrogen bond among water molecules will promote the water adsorption, while the adsorptions of CO₂ and CH₄ are only induced by the Van der Waals interaction, but the difference between adsorption density and bulk density of CO₂ and CH₄ decides the change of excess adsorption capacity.     

Computer calculations for thermal behavior of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Li<Subscript>2</Subscript>CO<Subscript>3</Subscript> melt

The thermal behavior of Na₂CO₃+Li₂CO₃ melt is studied by the method of thermodynamic simulation. The equilibrium compositions of the gas and salt phases are calculated at different temperatures in the initial argon atmosphere. Basic trends of the variation in the compositions of the melts and the gas phase above the melts in the presence of carbon are determined. The obtained results characterizing the stability of carbonate components in the melt are analyzed.     

A comparative study of Li<Subscript>2</Subscript>CO<Subscript>3</Subscript> modified carbon microbead anodes prepared by different synthetic routes for lithium-ion battery

Li₂CO₃ modified carbon microbead composites (LCO/CMB-T) with different covering amount are prepared by solvent evaporation and dipping method. LiCH₃COO are first used as lithium source, which can provide a precise control of Li₂CO₃ amount through varying dipping times or solution concentration. The morphology, structure, and covering amount are characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), and atomic absorption spectrometer (AAS). The dipping process can produce the samples with better surface coverage, more uniform coating, and higher Li₂CO₃ crystallinity, while the appropriate amount of Li₂CO₃ can help to decrease initial irreversible capacity and improve cell performance. Here, the sample with 1.07 % Li₂CO₃ prepared by dipping method shows the highest initial discharge capacity of 353.7 mAh g^?1 and coulombic efficiency of 89.5 %. The capacity retention is up to 82.1 % after 30 cycles.     

Synthesis of nanocrystalline SnO<Subscript>2</Subscript> in supercritical water

Nanocrystalline SnO₂ was synthesized in supercritical water at 385–415°C and 30 MPa (38–106 s residence time) in a tubular flow reactor from an aqueous solution of 0.1–0.4 M SnCl₄. The conversion rate was between 53 and 81%, but increased to 97.8% when 0.1 M NaOH was added. Nanoparticles were analyzed by a series of independent analytical techniques, including TEM, Raman, XRD, SEM, EDX and FT-IR. The initial size of the particles was about 3.7 nm. After calcination at 450°C for 2 h, the particle size increased to 4 nm. The particles were of low crystallinity, as indicated by the weak Raman and XRD signals. All particles were composed of Sn and O, as verified by the EDX spectra. The crystals were tetragonal, as confirmed by the weak XRD spectrum. After calcination at 600°C for 10 h, the particle size increased to 9 nm, while high crystallinity was confirmed by Raman and XRD analyses. All the crystals had the same structure, as indicated by TEM electron diffraction patterns. Using this one-step supercritical water process, nanoparticles of SnO₂ can be conveniently produced continuously in a flow reactor in less than 2 min.     

Oxidation of hydrogen sulfide and corrosion of stainless steel in gas mixtures containing H<Subscript>2</Subscript>S,O<Subscript>2</Subscript>, H<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript>

The composition of volatile and solid products of oxidation of hydrogen sulfide and stainless steel in gas mixtures containing H₂S, O₂, H₂O, and CO₂ has been determined using mass spectrometry, x-ray diffraction analysis, and scanning electron microscopy. It has been shown that holding an H₂S–O₂ mixture at 301 K results in prevailing formation of elemental sulfur and iron sulfides in the form of porous hygroscopic crust on the reactor wall surface. Formation of gas-phase sulfur causes self-acceleration of the oxidation of hydrogen sulfide; the resulting water triggers corrosion of the reactor wall. Heating of the resulting sulfur-sulfide crust in O₂ medium is accompanied by formation of SO₂ and heat release at T > 508 K. After heating of the H₂S–CO₂ mixture to 615 K, H₂ and COS were found in the volatile reactants; no noticeable corrosion of the reactor wall has been detected. It has been established that addition of O₂ to the H₂S–CO₂ mixture and its heating to 673 K leads to formation of ferrous sulfates. The mechanisms of the observed processes are discussed.     

Treatment of Cotton Fabrics by Ammonium Palmitate in a Supercritical CO<Subscript>2</Subscript> Medium

Experimental results on the solubility of ammonium palmitate as a potential fabric water-repellent agent in supercritical carbon dioxide (SC-CO₂)—pure and modified with acetone and dimethyl sulfoxide—are presented. The measurements are performed at temperatures 318.2 and 328.2 K in the pressure range from 10.0 to 32.5 MPa in a dynamic regime. The experimental solubility data are described using the Peng–Robinson equation of state. The results of treatment of various types of cotton fabrics by ammonium palmitate in SC-CO₂ are presented. The contact (wetting) angle of the treated samples is determined and the increase in their hydrophobicity is demonstrated.     

Impregnation of polymers with 2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl (TEMPONE) paramagnetic probe in sub- and supercritical CO<Subscript>2</Subscript>

The spin probe method is used to study the impregnation of polycarbonate (PC) based on bisphenol A, polyethylene oxide (PEO), and crosslinked acrylamide–acrylic acid copolymer (PAA) with organic molecules in sub- and supercritical CO₂ media. Electron spin resonance (EPR) data show that, at 196 bar and 307 K, 2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl (TEMPONE) paramagnetic spin probe molecules penetrate into the PC and PEO matrices, which are, respectively, in the glassy and elastic states under normal conditions. The degree of impregnation of PAA under these conditions is negligibly small. Estimates of the local concentration of probe molecules show that, in the PEO matrix, TEMPONE is distributed much more uniformly than in the PC matrix. Analysis of the effect of temperature on the shape of the EPR spectra of the radical in the polymer matrix shows that, under the same conditions, the mobility of TEMPONE molecules in the PEO matrix is much higher than in the PC matrix. The results suggest that the spin probe method is promising for studying the characteristics of macro- and micro-processes in polymer–supercritical fluid solvent–organic molecule ternary systems.     

Preparation and characterization of the polymer electrolyte system ENR50/PVC/EC/PC/LiN(CF<Subscript>3</Subscript>SO<Subscript>2</Subscript>)<Subscript>2</Subscript> for electrochemical device applications

Polymer electrolytes containing epoxidised natural rubber (ENR50)/poly(vinyl chloride) (PVC) blend as a polymer host, a solvent mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizer, and lithium imide, LiN (CF₃SO₂)₂, as a salt were studied. Polymer electrolytes that were obtained by solvent cast yielded solid dry rubbery films with a thickness range of 110–125 μm. Impedance spectroscopy, Fourier transform infra red (FTIR) spectroscopy, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were performed on these samples. The prepared solid polymer electrolytes exhibit ionic conductivities in the order 10⁻⁴ S cm⁻¹ at room temperature as expected. However, the physical properties of the electrolytes have improved significantly when optimal composition has been selected. Paper presented at the International Conference on Solid State Science and Technology 2006, Kuala Terengganu, Malaysia, Sept. 4–6, 2006.     

Preparation of RE<Subscript>2</Subscript>O<Subscript>2</Subscript>SO<Subscript>4</Subscript> (RE=La,Pr-Lu) microspheres from rare-earth-based infinite coordination polymers

Rare-earth-based infinite coordination polymer (RE-ICP) spheres with diameters ranging from 50 nm to 2 μm have been prepared using meso-2,3-dimercaptosuccinic acid (DMSA) as ligand under hydrothermal conditions. RE₂O₂SO₄ microspheres with similar morphology were obtained by calcining the corresponding RE-ICP spheres. However, as for Ce-ICP and Sc-ICP, CeO₂ and Sc₂O₃ were obtained. The products were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy, laser Raman spectrometry, and energy-dispersive X-ray spectrum. Elemental analysis and inductive coupled plasma atomic emission spectrometer were adopted to study the composition of the Eu-ICP. To explore their potential applications, several samples of the products were selected and their properties were investigated. The Eu-ICP and Eu₂O₂SO₄ microspheres give strong red emissions when excited with a 394-nm ultraviolet light. Furthermore, the Eu-ICP displays a high selectivity for Fe(III). The obtained CeO₂ has a strong absorption in the UV region and the Gd₂O₂SO₄ microspheres show paramagnetic behavior.

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Graphical abstract A series of RE₂O₂SO₄ microspheres were prepared using a coordination polymer precursor method.

     

Photoacoustic CO<Subscript>2</Subscript> sensor based on a DFB diode laser at 2.7 μm

We present a new detection scheme for carbon dioxide (CO₂) based on a custom-made room temperature distributed feedback (DFB) diode laser at 2.7 μm, currently representing one of the lasers with the highest emission wavelength of its kind. The detector's especially compact and simple set-up is based on photoacoustic spectroscopy (PAS). This method makes use of the transformation of absorbed modulated radiation into a sound wave. The sensor enables a very high detection sensitivity for CO₂ in the ppb range. Furthermore, the carefully selected spectral region as well as the narrow bandwidth and wide tunability of the single-mode laser ensure an excellent selectivity. Even measurements of different CO₂ isotopes can be easily performed. This enables applications in industrial sensing and medical diagnostics (e.g. ¹³C-breath tests).     

The effect of constant electric field on zirconium oxidation by supercritical CO<Subscript>2</Subscript>

The oxidation of zirconium by supercritical CO₂ (20.2 and 14.1 MPa, and 823 K) results in the formation of a layer of the monoclinic ZrO₂ and amorphous carbon. In the constant electric field (E = 293 kV/m) when a sample of zirconium is the anode, the formation of amorphous carbon leads to a growth of leakage current and a twelve-fold increase in the rate of zirconium oxidation.     

Density functional study of low-lying isomers of SiO<Subscript>4</Subscript>, GeO<Subscript>4</Subscript> and CO<Subscript>4</Subscript>, and their relation to tetrahedral solid phases

In silica (SiO₂) and in most silicates, atomic associations exist with composition SiO₄ and a structure with four O atoms in tetrahedral coordination around the Si atom. A similar feature is observed in germania (GeO₂) and some solids containing Ge instead of Si, although the number of phases containing GeO₄ tetrahedra is smaller. In contrast, and in spite of the fact that C is in the same column of the periodic table as Si and Ge, CO₂ is a molecular solid, and crystalline and amorphous phases of CO₂ showing CO₄ tetrahedra are only obtained under extremely high pressures. We have investigated the relation between free SiO₄, GeO₄ and CO₄ clusters and the tetrahedral associations found in the solids mentioned above. The lowest energy structure of those three free clusters is planar, but they have near-tetrahedral and distorted-tetrahedral isomers. The promotion energy from the planar structure to the distorted tetrahedral is low in SiO₄, large in CO₄, and intermediate in GeO₄. This correlates with the facility to form tetrahedral associations in the solids.     

Preparation and characterization of LiTi<Subscript>2</Subscript>O<Subscript>4</Subscript> anode material synthesized by one-step solid-state reaction

LiTi₂O₄ anode material for lithium-ion battery has been prepared by a novel one-step solid-state reaction method using Li₂CO₃, TiO₂, and carbon black as raw materials. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, and the determination of electrochemical properties show that the single phase of LiTi₂O₄ with spinel crystal structure is formed at 850?°C by this new method, and the lattice parameter is about 8.392?Å. The primary particle size of the LiTi₂O₄ powder is about 0.5–1.0 μm and its morphology is similar to a sphere. The lithium ion insertion voltage of LiTi₂O₄ anode material is about 1.50 V versus lithium metal, the initial discharge capacity is about 133.6 mAh g^-1, the charge–discharge voltage plateau is very flat, and no solid electrolyte interface film is formed when working potential is more than 1.0 V. The reaction reversibility and the cycling stability are excellent, and the high rate performance is good.     

NO<Subscript>2</Subscript>-sensing properties of La<Subscript>0.65</Subscript>Sr<Subscript>0.35</Subscript>MnO<Subscript>3</Subscript> synthesized by self-propagating combustion

Ultrafine-structure La_0.65Sr_0.35MnO₃ (LSM) powders synthesized by self-propagating combustion method have been used to fabricate sensing electrodes (SEs) for NO₂ mixed-potential sensors based on yttria-stabilized zirconia (YSZ). This type of sensor was found to provide better NO₂ sensitivity at 500 °C than sensors with LSM powders synthesized by traditional solid-state methods. The response values of the sensor have good linear relationship (sensitivity 36.6 mV/decade and linear fit 0.99) with the logarithm of NO₂ concentration varying from 30 to 500 ppm. The influence of sintering temperature (1000, 1100, 1200, and 1300 °C) on sensor response was also examined and was found to have a significant effect on the morphology of LSM-SEs. Moreover, in the presence of NO, CO₂, CO, and NO₂, the sensor exhibited good NO₂ selectivity.     

Sorption and Diffusion of Supercritical Carbon Dioxide in a Biodegradable Polymer

A gravimetric method was used to study the sorption and diffusion of supercritical carbon dioxide in a temperature range from 40°C to 80°C and a pressure range from 8.0 to 18.0 MPa in a biodegradable polymer, namely poly(butylene adipate-co-terephthalate) (PBAT). The PBAT presented Fickian behavior and Fick's diffusion model was applied to determine the amount of carbon dioxide present in the samples after a predetermined exposure time as well as the diffusion coefficients. The variations of diffusion coefficients of CO₂ for the sorption under supercritical conditions and desorption at ambient conditions as well as equilibrium sorption amounts of CO₂ with variations of pressure and temperature were determined and compared.     

Self-Broadening and Carbon-Dioxide Broadening of Lines of the H<Subscript>2</Subscript>S Molecule

Carbon-dioxide-broadening coefficients and self-broadening coefficients of lines of the main isotopic modification of Н₂S are estimated on the basis of literature data. The J′-dependences of the above line-profile parameters of the hydrogen-sulfide molecule are examined. In the case of CO₂ broadening, the half-widths of lines are calculated by a semiempirical method based on a parametric modification of the impact semiclassical model; the model parameters were determined from the fit to experimental data.