Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

A combined spectroscopic and theoretical study of dibutyltin diacetate and dilaurate in supercritical CO2

Two organotin catalysts, namely, dibutyltin dilaurate (DBTDL) and dibutyltin diacetate (DBTDA), commonly used in the synthesis of polyurethanes, have been investigated combining vibrational spectroscopic measurements with molecular modeling. The structure and vibrational spectra of the DBTDA molecule have been simulated using density functional theory. Thus, because of the Sn...O interactions, the lowest energy conformer reveals an asymmetrically chelated structure of the acetate groups with a C2v symmetry. The experimental IR spectra of DBTDA and DBTDL diluted in carbon tetrachloride and in supercritical CO2 show unambiguously that these molecules adopt the asymmetrically chelated conformation in the solvent. A new attribution of the main peaks constituting the respective IR spectra of the catalysts could be carried out. Finally, from the IR spectra of the two catalysts diluted in supercritical CO2 reported as a function of time, it was found that both molecules react slightly with CO2. However, their spectrum remains unchanged at the earliest stage of the polymerization, indicating that these molecules preserve a catalytic activity similar to that noted in conventional organic solvent.     

Poly(<Emphasis Type="Italic">n</Emphasis>-octyl methacrylate) viscosity index improver: Kinetic study via on-line <Superscript>1</Superscript>H-NMR technique

The free radical solution polymerization of n-octyl methacrylate has been studied in benzene-d ₆ in the presence of 2,2′-azobisisobutyronitrile as thermal initiator. An on-line nuclear magnetic resonance spectroscopy was applied to record the reaction data and to determine the monomer conversion at different times during the polymerization reaction. Effect of monomer and initiator concentration as well as reaction temperature on polymerization rate was studied. The order of the reaction with respect to initiator (0.45) was consistent with the classical kinetic rate equation, while the order of reaction with respect to monomer (1.87) was much greater than unity. An overall activation energy (E _a = 53.8 kJ/mol) was obtained over the temperature range 328?338 K. Also, the efficiency of the synthesized poly(n-octyl methacrylate) for improving the viscosity index of the lube oil was investigated.     

On the solutions of a higher‐order difference equation in terms of generalized Fibonacci sequences

This paper deals with the solutions, stability character, and asymptotic behavior of the difference equation where and the initial values x_?k,x_{?k + 1},…,x₀ are nonzero real numbers, such that their solutions are associated to Horadam numbers. Copyright © 2015 John Wiley & Sons, Ltd.     

Determination of gasoline and diesel residues on wool,silk, polyester and cotton materials by SPME–GC–MS

The identification of ignitable liquids is very important and challenging aspect in arson crime investigations. The detection of gasoline and diesel fuel components using solid phase micro-extraction prior to gas chromatography–mass spectrometry for the forensic analysis of fire debris has been carried out. Previous works show that the absorption characteristics of the substrate are one of the most important factors in determining the evaporation rate of the accelerants. In order to determine the presence of the fuel residues, four of the most common substrate materials were tested in this work; wool, cotton, silk and polyester. The obtained results indicate that both gasoline and diesel fuel accelerants persisted longer on wool and silk than on the other selected substrates. Such information illustrates the influence of fuel persistence times after extinguishing and the best materials to be scanned for ignitable liquids at the fire scene.     

Quantification of high-power ultrasound induced damage on potato starch granules using light microscopy

A simple light microscopic technique was developed in order to quantify the damage inflicted by high-power low-frequency ultrasound (0-160 W, 20 kHz) treatment on potato starch granules in aqueous dispersions. The surface properties of the starch granules were modified using ethanol and SDS washing methods, which are known to displace proteins and lipids from the surface of the starch granules. The study showed that in the case of normal and ethanol-washed potato starch dispersions, two linear regions were observed. The number of defects first increased linearly with an increase in ultrasound power up to a threshold level. This was then followed by another linear dependence of the number of defects on the ultrasound power. The power threshold where the change-over occurred was higher for the ethanol-washed potato dispersions compared to non-washed potato dispersions. In the case of SDS-washed potato starch, although the increase in defects was linear with the ultrasound power, the power threshold for a second linear region was not observed. These results are discussed in terms of the different possible mechanisms of cavitation induced-damage (hydrodynamic shear stresses and micro-jetting) and by taking into account the hydrophobicity of the starch granule surface.     

Shear localisation in stirred yoghurt

The shear flow behaviour of stirred yoghurt in the cone-and-plate and cylindrical Couette geometries was studied using diffusing wave spectroscopy (DWS) and nuclear magnetic resonance (NMR) velocimetry. Differences between the transmission and backscattering DWS correlations suggest the formation of a high shear rate band near the surface of a moving cone of a cone-and-plate geometry at low shear rates. At higher shear rates, homogeneous shear flow is indicated. NMR velocimetry unambiguously demonstrated that a high shear rate band forms at the moving inner wall of a cylindrical Couette geometry at low shear rates. At intermediate shear rate, a high shear rate band is formed at the stationary outer wall and plug-like flow is observed mid-gap. At higher shear rates, homogeneous shear flow is observed. Slip is seen at both walls. The three flow regimes appear to correlate loosely with transitions in the pseudo-steady-state flow curve and may reflect a break-up of the protein aggregates observed with confocal microscopy.     

Croissance des Solutions des D-Modules algébriques holonomes – (Growth of solutions of holonomic algebraic D-modules)

We show that the cohomology of complexes of solutions of exponantial type associated to holonomic algebraic D-modules is constructible. We also compute the Euler–Poincaré index of such complexes.     

Solid-liquid equilibria and purity determination for binary n-alkane + naphthalene systems

Mixtures of heavy aromatics with high aliphatics are important in the formation of asphaltenes in the oil industry.This work reports binary solid-liquid equilibria for naphtalene + eicosane, +pentacosane, +hexatriacontane mixtures by differential scanning calorimetry. Results are compared with those from modified UNIFAC (Larsen and Gmehling versions) and ideal predictions. Finally, we determine the purity according to van’t Hoff equation. Results are in good agreement with values given by ultraviolet spectrophotometry.