Niobium on BEA Dealuminated Zeolite for High Selectivity Dehydration Reactions of Ethanol and Xylose into Diethyl Ether and Furfural.

In this work, we investigated the role of solid-state dealumination by (NH4)2SiF6 (25% Al removal and 13% Si insertion), the impregnation of niobium (10, 18, and 25 wt. %) on dealuminated *BEA (DB) zeolite and their catalytic properties in ethanol and xylose transformations. Among all the studied catalysts, 18%Nb-DB showed increased mesoporosity and external areas. A leveling effect in the number and strength of the proposed two sites (Brønsted and Lewis) present in the catalyst (n1 = 0.24 mmol g-1, -ΔH1 = 49 kJ mol-1, and n2 = 0.20 mmol g-1, -ΔH2 = 42 kJ mol-1) in the catalyst 18%Nb-DB, might be responsible for its good activity. This catalyst presented the highest selectivity for diethyl ether, DEE (97%) with 61% conversion after 50 ethanol pulses at 230 °C (turnover number, TON DEE = 1.15). These features allowed catalytically fruitful bonding of the ethanol molecules to the neighboring sites on the channels, facilitating bimolecular ether formation through a possible SN2 mechanism. The same catalyst was active and selective for transformation of xylose at 180 °C, showing 64% conversion and 51% selectivity for furfural (TON Furfural = 24.7) using water as a green solvent.

Corrigendum to "Preparation of PLA blends by polycondensation of D,L-lactic acid using supported 12-tungstophosphoric acid as a heterogeneous catalyst" [Heliyon 5 (5) (May 2019) e01810].

[This corrects the article DOI: 10.1016/j.heliyon.2019.e01810.].

Preparation of PLA blends by polycondensation of D,L-lactic acid using supported 12-tungstophosphoric acid as a heterogeneous catalyst.

Poly(lactic acid) (PLA) is a significant polymer that is based on renewable biomass resources. The production of PLA by polycondensation using heterogeneous catalysis is a focus for sustainable and economical processes. A series of samples comprising 12-tungstophosphoric acid (H3PW) supported on activated carbon, silica, and alumina induced the catalytic polymerization of D,L-lactic acid to form blends of PLA. The catalysts were characterized by multiple techniques to confirm the integrity of the Keggin anion as well as the acidity, which is the key property for relating structure to activity. The best reaction conditions were established for H3PW/C and tested for the other supported catalysts. The obtained polymer was a blend that was characterized as an enantiomeric excess (ee) of as much as 95% L-PLA (PLLA) with a mass average molar mass (M w ) of approximately 14,900 daltons. The role of H3PW in these polymerizations was demonstrated, i.e., without the Keggin acid, only oligomeric units (M w < 10,000 daltons) could be obtained. Additionally, inverse relationships between the M w of PLA and the enthalpy (-ΔH) of the strongest sites of the catalysts were distinguished, i.e., PLAMw-H3PW/C > PLAMw-H3PW/Al2O3 > PLAMw-H3PW/SiO2, whereas the acidity (-ΔH) order was as follows: H3PW/SiO2 > H3PW/Al2O3 > H3PW/C. These findings could be attributed to the correct tuning of strength and the accessibility of the sites to produce longer polymeric chains.

Tuning the Biginelli reaction mechanism by the ionic liquid effect: the combined role of supported heteropolyacid derivatives and acidic strength.

Herein, a combination of heteropolyacids and ionic liquids as a catalytic system was studied for the Biginelli multicomponent reaction; the positive ionic liquid effect associated with the acidic strength of zeolite-supported heteropolyacids made this combination an efficient catalytic system for the multicomponent synthesis of 3,4-dihydropyrimidin-2(1H)-one/thione derivatives. The acidic strength effect was evaluated, and a range was determined in which the reaction provided better results. The mechanism of the reaction was also investigated in the presence and absence of ionic liquids, and two features of paramount importance were revealed: the mechanism could be tuned to proceed through only one reaction path among three possibilities and the kinetics of the reaction was significantly faster in the presence of an ionic liquid.

Analytical evaluation of BEA zeolite for the pre-concentration of polycyclic aromatic hydrocarbons and their subsequent chromatographic analysis in water samples.

The analytical performance of BEA - a commercial zeolite - is evaluated for the pre-concentration of fifteen Environmental Protection Agency - polycyclic aromatic hydrocarbons and their subsequent HPLC analysis in tap and lake water samples. The pre-concentration factors obtained with BEA have led to a method with excellent analytical figures of merit. One milliliter aliquots were sufficient to obtain excellent precision of measurements at the parts-per-trillion concentration level with relative standard deviations varying from 4.1% (dibenzo[a,h]anthracene) to 13.4% (pyrene). The limits of detection were excellent as well and varied between 1.1 (anthracene) and 49.9 ng L(-1) (indeno[1,2,3-cd]pyrene). The recovery values of all the studied compounds meet the criterion for regulated polycyclic aromatic hydrocarbons, which mandates relative standard deviations equal or lower than 25%. The small volume of organic solvents (100 µL per sample) and amount of BEA (2 mg per sample) makes sample pre-concentration environmentally friendly and cost effective. The extraction procedure is well suited for numerous samples as the small working volume (1 mL) facilitates the implementation of simultaneous sample extraction. These are attractive features when routine monitoring of numerous samples is contemplated.

Indirect determination of dichlorodiphenyltrichloroethane (DDT) after dechlorination with magnesium/palladium bimetallic particles and potentiometric measurements.

Determination of chlorine ions of pesticides was performed after dechlorination reaction using a palladium/magnesium system. Chlorine ions were quantified by potentiometry with ion-specific electrode. Rates of dechlorination of 100 microg of DDT as a function of reaction time and percent (wt/wt) of palladium deposited on the magnesium particles were determined. The best reaction conditions to DDT dechlorination were achieved with an acetone/water (1:1) solution and DDT reaction with a 0.27% (wt/wt) palladium/magnesium bimetallic system at room temperature for 10 min. The detection limit was of 0.24 microg/mL. This low cost method showed an efficiency of 92% in determining chlorine ions derived from DDT, it is fast, requiring no specialized laboratory equipment.

Comparative adsorption studies of indigo carmine dye on chitin and chitosan.

The adsorption of indigo carmine dye onto chitin and chitosan from aqueous solutions was followed in a batch system. The ability of these materials to adsorb indigo carmine dye from aqueous solution was followed through a series of adsorption isotherms adjusted to a modified Langmuir equation. The maximum number of moles adsorbed was 1.24 +/- 0.16 x 10(-5) and 1.54 +/- 0.03 x 10(-4) mol g(-1) for chitin and chitosan, respectively. The same interactions were calorimetrically followed and the thermodynamic data showed exothermic enthalpic values of -40.12 +/- 3.52 and -29.25 +/- 1.93 kJ mol(-1) for chitin and chitosan, respectively. Gibbs free energies for the two adsorption processes of indigo carmine dye presented a positive value for chitin and a negative one for chitosan, reflecting that dye/surface interactions are thermodynamic favorable for chitosan and nonspontaneous for chitin at 298.15 K. The interaction processes were accompanied by an increase of entropy value for chitosan (90 +/- 6 J mol(-1)K(-1)) and a decrease for chitin (-145 +/- 13 J mol(-1)K(-1)). Thus, dye/chitosan interaction showed favorable enthalpic and entropic processes, reflecting thermodynamic stability of the formed complex, while dye/chitin interaction showed an exothermic enthalpic value and a highly nonfavorable entropic effect, resulting in a nonspontaneous thermodynamic system.

Calorimetric studies of the association of chitin and chitosan with sodium dodecyl sulfate.

The interaction of hydrophobic chitin and chitosan with sodium dodecyl sulfate (SDS) has been studied by titration calorimetry at 298.15K. The nature of interaction of the surfactant and biopolymers was followed by enthalpy interaction profiles. The mixing enthalpy curves were determined by mixing SDS solutions above their critical micelle concentration with chitin and chitosan suspensions in different concentrations. The Gibbs free energy of aggregation values were -23.21, -22.71 and -21.53 kJ mol(-1) for chitin in 0.02, 0.05 and 0.1% concentration, respectively, and 28.30, 24.38 and 24.20 kJ mol(-1) for chitosan in 0.02, 0.05 and 0.1% concentration, respectively. The critical aggregation concentration (cac) obtained by calorimetric data gave 6.32, 7.07 and 9.14 mmol kg(-1) in 0.02, 0.05 and 0.1% concentration, respectively, for chitin and 2.09, 4.91 and 5.11 mmol kg(-1) for chitosan in 0.02, 0.05 and 0.1% concentration, respectively.