Identifying signatures of thermal and non-thermal reaction pathways in plasmon induced H2 + D2 exchange reaction

In this work we demonstrate a strategy for identifying experimental signatures of thermal and non-thermal effects in plasmon mediated heterogeneous catalytic chemistry, a topic widely debated and discussed in the literature. Our method is based on monitoring the progress of plasmon-induced (or thermally-driven) reaction, carried out in a closed system, all the way to equilibrium. Initial part of evolution of the reaction provides information about kinetics, whereas at later times the equilibrium concentrations provide information about effective temperature at the reaction sites. Combining these two pieces of information we estimate the activation energies. Using this strategy on H 2 (g) + D 2 (g) <-->2 HD(g) isotope exchange reaction, catalyzed by Au nanoparticles under thermally-driven and light-induced conditions, we estimate the activation energies to be 0.75 ± 0.02 eV and 0.21 ± 0.02 eV, respectively. These vastly different activation energies observed are interpreted as a signature of different reaction pathways followed by the system under thermally-driven and light-induced conditions.

Identifying signatures of thermal and non-thermal reaction pathways in plasmon induced H2 + D2 exchange reaction

In this work we demonstrate a strategy for identifying experimental signatures of thermal and non-thermal effects in plasmon mediated heterogeneous catalytic chemistry, a topic widely debated and discussed in the literature. Our method is based on monitoring the progress of plasmon induced (or thermally driven) reaction, carried out in a closed system, all the way to equilibrium. Initial part of evolution of the reaction provides information about kinetics, where as at later times the equilibrium concentrations provide information about effective temperature at the reaction sites. Combining these two pieces of information we estimate the activation energies. Using this strategy on H2 (g) + D2 (g) <--> 2 HD(g) isotope exchange reaction, catalyzed by Au nanoparticles under thermally driven and light induced conditions, we estimate the activation energies to be 0.75 ± 0.02 and 0.21 ± 0.02, respectively. These vastly different activation energies observed are interpreted as signatures of different reaction pathways followed by the system under thermally driven and light induced conditions.

pH-metric method for determining the solubility and solubility products of slightly soluble hydroxides and acids

In this paper, original methods for determining such thermodynamic characteristics as solubility K S0 product (KS) or the activity product ( )of slightly soluble hydroxides and acids are communicated. Developed methods for determining KS and solubility S are based only on the pH values of the saturated aqueous solution for a known initial composition of the heterogeneous mixture and the equilibrium constants of an arbitrary set of possible side reactions in the aqueous natural systems. The determination of solubility S and solubility product KS is also possible in the presence of other hydroxides or acids of known concentrations. Deduced equations allow the calculation of such characteristics, as the equilibrium concentrations of the components of slightly soluble compounds in aqueous phase and the degree of precipitation γ of the solid phase for various initial concentrations of the components of the heterogeneous mixture which are known in the process of preparing the mixture, requiring only experimental pH values of a saturated solution. From the known experimental pH data, S and KS were calculated for a series of hydroxides and acids of arbitrary composition. The obtained results correlated well with the known tabular values. Analysis of a number of real systems illustrated the deduced expressions, including calculations and theoretical explanations.

The Electronic Structural and Defect-Induced Absorption Properties of a Ca2B10O14F6 Crystal

Comprehensive ab initio electronic structure calculations were performed for a newly developed deep-ultraviolet (DUV) non-linear optical (NLO) crystal Ca2B10O14F6 (CBOF) using the first principle method. Fifteen point defects including interstitial, vacancy, antisite, Frenkel, and Schottky of Ca, O, F, and B atoms in CBOF were thoroughly investigated as well as their effects on the optical absorption properties. Their formation energies and the equilibrium concentrations were also calculated by ab initio total energy calculations. The growth morphology was quantitatively analyzed using the Hartman–Perdok approach. The formation energy of interstitial F (Fi) and antisite defect OF were calculated to be approximately 0.33 eV and 0.83 eV, suggesting that they might be the dominant defects in the CBOF material. The absorption centers might be induced by the O and F vacancies (VF, VO), interstitial B and O (Oi, Bi), and the antisite defect O substitute of F (OF), which might be responsible for lowering the damage threshold of CBOF. The ionic conductivity might be increased by the Ca vacancy (Vca), and, therefore, the laser-induced damage threshold decreases.

Organobeidellites for Removal of Anti-Inflammatory Drugs from Aqueous Solutions

Diclofenac (DC) and ibuprofen (IBU) are widely prescribed non-steroidal anti-inflammatory drugs, the consumption of which has rapidly increased in recent years. The biodegradability of pharmaceuticals is negligible and their removal efficiency by wastewater treatment is very low. Therefore, the beidelitte (BEI) as unique nanomaterial was modified by the following different surfactants: cetylpyridinium (CP), benzalkonium (BA) and tetradecyltrimethylammonium (TD) bromides. Organobeidellites were tested as potential nanosorbents for analgesics. The organobeidellites were characterized using X-ray powder diffraction (XRD), Infrared spectroscopy (IR), Thermogravimetry and differential thermal analysis (TG/DTA) and scanning microscopy (SEM). The equilibrium concentrations of analgesics in solution were determined using UV-VIS spectroscopy. The intercalation of surfactants into BEI structure was confirmed both using XRD analysis due to an increase in basal spacing from 1.53 to 2.01 nm for BEI_BA and IR by decreasing in the intensities of bands related to the adsorbed water. SEM proved successful in the uploading of surfactants by a rougher and eroded organobeidellite surface. TG/DTA evaluated the decrease in dehydration/dehydroxylation temperatures due to higher hydrophobicity. The Sorption experiments demonstrated a sufficient sorption ability for IBU (55–86%) and an excellent ability for DC (over 90%). The maximum adsorption capacity was found for BEI_BA-DC (49.02 mg·g−1). The adsorption according to surfactant type follows the order BEI_BA > BEI_TD > BEI_CP.

Calculation of the Gibbs–Donnan factors for multi-ion solutions with non-permeating charge on both sides of a permselective membrane

Separation of two ionic solutions with a permselective membrane that is impermeable to some of the ions leads to an uneven distribution of permeating ions on the two sides of the membrane described by the Gibbs–Donnan (G–D) equilibrium with the G–D factors relating ion concentrations in the two solutions. Here, we present a method of calculating the G–D factors for ideal electroneutral multi-ion solutions with different total charge of non-permeating species on each side of a permselective membrane separating two compartments. We discuss some special cases of G–D equilibrium for which an analytical solution may be found, and we prove the transitivity of G–D factors for multi-ion solutions in several compartments interconnected by permselective membranes. We show a few examples of calculation of the G–D factors for both simple and complex solutions, including the case of human blood plasma and interstitial fluid separated by capillary walls. The article is accompanied by an online tool that enables the calculation of the G–D factors and the equilibrium concentrations for multi-ion solutions with various composition in terms of permeating ions and non-permeating charge, according to the presented method.

A Parameter Study of Ultrasound Assisted Enzymatic Esterification

This work is focused on the study of esterification parameters for the ultrasound assisted synthesis of isoamyl acetate catalyzed by lipase Lipozyme 435 in a continuous loop reactor. Investigating the influence of different parameters shows that a higher concentration of ester (462 mg/gmixture) can be obtained at temperature 50 °C, flow rate 0.16 mL/min. The best ultrasonication conditions are: continuously applied sonication for a short time (20 minutes), ultrasound power 32 mW, and amplitude 20 %. The enzyme can be successfully reused tree times without loss of enzyme activity. Reaction kinetics for isoamyl acetate ultrasound assisted production showed that satisfactory reaction concentration (close to the equilibrium concentrations) could be reached in short reaction times (2 h). Ultrasound assisted enzymatic esterification is consequently a cleaner and a faster process.

Investigation of Regeneration Mechanisms of Aged Solar Salt

The scope of our study was to examine the potential of regeneration mechanisms of an aged molten Solar Salt (nitrite, oxide impurity) by utilization of reactive gas species (nitrous gases, oxygen). Initially, aging of Solar Salt (60 wt% NaNO3, 40 wt% KNO3) was mimicked by supplementing the decomposition products, sodium nitrite and sodium peroxide, to the nitrate salt mixture. The impact of different reactive purge gas compositions on the regeneration of Solar Salt was elaborated. Purging the molten salt with a synthetic air (p(O2) = 0.2 atm) gas stream containing NO (200 ppm), the oxide ion concentration was effectively reduced. Increasing the oxygen partial pressure (p(O2) = 0.8 atm, 200 ppm NO) resulted in even lower oxide ion equilibrium concentrations. To our knowledge, this investigation is the first to present evidence of the regeneration of an oxide rich molten Solar Salt, and reveals the huge impact of reactive gases on Solar Salt reaction chemistry.

Adsorption of metal ions in red marine algae Lithothamnium calcareum in the treatment of industrial effluents

This study investigated the adsorption capacity of the elements Chromium (Cr), Manganese (Mn) and Zinc (Zn) to marine algae Lithothamnium calcareum by means of adsorption kinetics and batch adsorption tests, with a view to the development of a simple technique for the treatment of effluents that have a high concentration of metal ions. The algae was sieved, washed and subjected to treatment. In the adsorption kinetics, 0.2 g of algae was weighed, an amount transferred to 125 mL Erlenmeyer flasks, to which was added 15 mL of solution with a concentration of 5 mg L-1 of the metal ion. The flasks were stirred at 60 rpm for 240 minutes. In batch adsorption, 0.2 g of algae was weighed, amount transferred to 125 mL Erlenmeyer flasks, to which was added 15 mL of solution with concentrations of 5, 10, 20, 50, 100, 250 e 500 mg L-1 of the metal ion. The flasks were stirred at 60 rpm for 24 hours. In the two tests, the supernatant solutions collected were centrifuged at 2000 rpm for 5 minutes and the equilibrium concentrations of metal ions were determined by atomic absorption spectrometry. It was found that, in 240 minutes of contact, the Lithothamnium calcareum removed 15.5% of Cr, 33.0% of Mn and 8.0% of Zn in solution; and that in 24 hours of contact, at a concentration of 5 mg L-1, it removed 0.4% of Cr, 52.5% of Mn and 92.6% of Zn; and, at a concentration of 500 mg L-1, it removed 20.0% of Cr, 22.6% of Mn and 40.8% of Zn. The results showed that the Lithothamnium calcareum submitted to thermochemical treatment presented potential for use in the adsorption of Cr, Mn and Zn.