Photoelectrocatalytic degradation of high-density polyethylene microplastics on TiO2-modified boron-doped diamond photoanode.

Microplastic (MP) accumulation in the environment is accelerating rapidly, which has led to their effects on both the ecosystem and human life garnering much attention. This study is the first to examine the degradation of high-density polyethylene (HDPE) MPs via photoelectrocatalysis (PEC) using a TiO2-modified boron-doped diamond (BDD/TiO2) photoanode. This study was divided into three stages: (i) preparation of the photoanode through electrophoretic deposition of synthetic TiO2 nanoparticles on a BDD electrode; (ii) characterization of the modified photoanode using electrochemical, structural, and optical techniques; and (iii) degradation of HDPE MPs by electrochemical oxidation and photoelectrocatalysis on bare and modified BDD electrodes under dark and UV light conditions. The results indicate that the PEC technique degraded 89.91 ± 0.08% of HDPE MPs in a 10-h reaction and was more efficient at a lower current density (6.89 mA cm-1) with the BDD/TiO2 photoanode compared to electrochemical oxidation on bare BDD.

Effect of size and amount of sugarcane fibers on the properties of baked foams based on plantain flour.

Baked foams made with plantain flour (PF) and sugarcane fiber (SF) were characterized by calorimetric, mechanical, physicochemical and structural techniques in order to assess the results induced by different sugarcane concentrations and fiber size on the structure of baked foams. The addition of SF to the baked samples increased their hydrophobic properties. Thermal conductivity (TC) decreased when the concentration of SF was 10 g and 7.5 g in the baked foams. The density of the biodegradable baked foams (BBFs) decreased with decreasing concentrations of SF, observing an inverse behavior in water vapor permeability (WVP) and solubility properties. The mechanical properties of the baked foams were more influenced by the concentration of SF than by the size of SF, obtained from different sieves. The scanning electron microscopy cross-sectional images of the BBFs showed that the size of SF affected the size and number of the internal cells in the BBFs.

Kinetics of thermal degradation and lifetime study of poly(vinylidene fluoride) (PVDF) subjected to bioethanol fuel accelerated aging.

PVDF was prepared by compression molding, and its phase content/structure was assessed by WAXD, DSC, and FTIR-ATR spectroscopy. Next, PVDF samples were aged in bioethanol fuel at 60 °C or annealed in the same temperature by 30 ─ 180 days. Then, the influence of aging/annealing on thermal stability, thermal degradation kinetics, and lifetime of the PVDF was investigated by thermogravimetric analysis (TGA/DTG), as well as the structure was again examined. The crystallinity of ~41% (from WAXD) or ~49% (from DSC) were identified for unaged PVDF, without significant changes after aging or annealing. This PVDF presented not only one phase, but a mixture of α-, ß- and γ-phases, α- and ß-phases with more highlighted vibrational bands. Thermal degradation kinetics was evaluated using the non-isothermal Ozawa-Flynn-Wall method. The activation energy (E a ) of thermal degradation was calculated for conversion levels of α = 5 ─ 50% at constant heating rates (5, 10, 20, and 40 °C min─1), α = 10% was fixed for lifetime estimation. The results indicated that temperature alone does not affect the material, but its combination with bioethanol reduced the onset temperature and E a of primary thermal degradation. Additionally, the material lifetime decreased until about five decades (T f = 25 °C and 90 days of exposition) due to the fluid effect after aging.

Discerning the thermal cyclotrimerizations of fluoro- and chloroacetylenes through ELF, NBO descriptors and QTAIM analysis: pseudodiradical character.

In this study the thermal cyclotrimerization reactions of fluoro- and chloroacetylenes involving regioselectively stepwise {2 + 2} and stepwise {4 + 2} cycloadditions were studied using the topological analysis of the electron localization function (ELF), the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. These methodologies have shown that the electronic reorganization in the regioselectively stepwise {2 + 2} and stepwise {4 + 2} cycloadditions may be considered as {2n+2n} and {2π+2n} pseudodiradical process, respectively. Finally, the last phase of this thermal reaction can be understood as an electronic migration process under the pseudodiradical character in the thermal ring-opening reaction, with the subsequent formation of reaction products. In this sense, new insights are reported on the electronic behavior in the bond formation in the thermal cyclotrimerization of fluoroacetylene.

Exploring the nature of the interactions between the molecules of the sodium dodecyl sulfate and water in crystal phases and in the water/vacuum interface.

The nature of the interaction between the molecules of the sodium dodecyl sulfate surfactant forming two crystal phases, one anhydrous, NaC12H25O4S and the other, NaC12H25O4S.H2O, hydrated with one water molecule for unit cell, has been studied in detail using the quantum theory of atoms in molecules and a localized electron detector function. It was found that for the anhydrous crystal, the head groups of the surfactant molecules are linked into a head-to-head pattern, by a bond path network of Na-O ionic bonds, where each Na+ atom is attached to four S O 4 - groups. For the hydrated crystal, in addition to these four bonds for Na+, two additional ones appear with the oxygen atoms of the water molecules, forming a bond paths network of ionic Na-O bonds, that link the Na+ atoms with the S O 4 - groups and the H2O molecules. Each H2O molecule is bonded to two S O 4 - groups via hydrogen bonds, while the S O 4 - groups are linked to a maximum of four Na+ atoms. The phenomenon of aggregation of the sodium dodecyl sulfate molecules at the liquid water/vacuum interface was studied using NVT molecular dynamics simulations. We have found that for surfactant aggregates, the Na+ ions are linked to a maximum of three SO4 - groups and three water molecules that form Na-O bonds. Unlike hydrated crystal, each of the O atoms that make these Na-O bonds is linked to only one Na+ ion. Despite these differences, like the crystal phases, the surfactant molecules tend to form a head-to-head network pattern of ionic Na-O bonds that link their heads. The present results indicate that the clustering of anionic surfactant at the water/vacuum interface is a consequence of the electrostatic alignment of the cationic and anionic groups as occurs in the crystalline phases of sodium dodecyl sulfate.

Effects of palm biodiesel and blends of biodiesel with organic acids on metals.

This paper presents the corrosion behavior studies of five metallic materials used in auto part manufacturing exposed to pure palm biodiesel (B100) and palm biodiesel mixed with acidic species commonly found in biodiesel. Samples of AISI-SAE 1005 carbon steel, AISI-SAE 304 stainless steel, tin, aluminum and copper were exposed to a temperature of 45 °C for 12 months. The highest corrosion rates were present in totally immersed copper (B100-acetic acid blend) and in carbon steel (B100-oleic acid blend). The most corrosive blends for the metallic materials were B100-linoleic acid, B100-oleic acid and B100-acetic acid. The efficacy of two corrosion inhibitors, ethylenediamine (EDA) and tert-butylamine (TBA) increased as a function of exposure time. The characterization tests allowed the detection of different species, in the products of steel corrosion, associated with, lepidocrocite, ferrihydrite, magnetite, and some iron carbonates. In turn, cuprite, malachite, azurite, and some copper carbonates were found on the copper samples. Such corrosion products formed protective layers on the surface of the metals, which is reflected in a decrease in corrosion rates over time.

Fe(III)-polyhydroxy cations supported onto K10 montmorillonite for removal of phosphate from waters.

Since phosphate is strongly related to eutrophication of environmental waters, several research groups quest for materials that can efficiently remove phosphate from wastewaters before it contaminates lakes and reservoirs. In the present work, a commercial clay mineral (K10 montmorillonite) modified with Fe3+ polyhydroxy cations was investigated as an adsorbent for phosphate. The incorporation of the polycations did not alter the main conformational characteristics of the montmorillonite, as verified by specific surface area measurements, X-ray diffractometry, FTIR, electron microscopy, and zeta potential titrations. On the other hand, the materials supporting Fe3+ polyhydroxy cations exhibited a significant enhancement of adsorption capacity, as determined by Langmuir-Freundlich isotherms, from 39 ± 2 to 104 ± 15 µmol g-1. The different ratios of OH- to Fe3+ did not affect the adsorption capacities. The adsorption kinetics was best described by the pseudo 2nd order model, approaching the equilibrium after 120 min of contact time. A variation of pH between 4.6 and 8.5 did not affect the adsorption percentages. The adsorption capacities increased with the increase of the ionic strength, thus suggesting that the formation of inner-sphere complexes prevails over electrostatic interactions as the adsorption mechanism. The materials removed phosphate from three polluted water samples having phosphate concentrations between 0.0919 and 1.211 mg L-1. The remaining phosphate concentration was below the limit of quantification of the analytical method (0.063 mg L-1 in P, or 2.0 µmol L-1). The presence of 10 mg L-1 humic of fulvic acid did not affect the performance of the materials. In conclusion, the modification of clay minerals with Fe3+ polyhydroxy cations is useful in producing low-cost adsorbents for phosphate.

Detection of carvacrol in essential oils by electrochemical polymerization.

Carvacrol (Carv) and thymol (TOH), components of essential oils, are known by their antimicrobial and antioxidant activity. However, Carv but not TOH seems to be the responsible of anti-inflammatory and inhibition of Cu corrosion properties. Since Carv and TOH are positional isomers, their identification is tricky and GC-MS is usually required. To find simple and inexpensive methods that allow the detection of Carv in presence of TOH (e.g. essential oils), cyclic voltammetry and chronoamperometry tests using Pt and Cu as electrodes in TOH and Carv containing mixtures and essential oils were made. Electrochemical and ATR-FTIR results show that pure phytocompounds and mixtures lead to the formation of polymeric layers on both metallic surfaces. Results show that only Cu is suitable for Carv detection. Potentiostatic and potentiodynamic detection is simple and conclusive in Carv + TOH mixtures and in essential oils due to the formation of a homogeneous blocking Carv electropolymeric layer on Cu.

Chrysotile asbestos treated with phosphoric acid as an adsorbent for ammonia nitrogen.

The purpose of this study was to find an alternative application for chrysotile asbestos, given that there is a complete structure of extraction and production of this class of serpentine minerals, but its use is banned for many applications. The idea was to obtain a compound that could immobilize phosphate by triggering a reaction between the magnesium oxide and hydroxide contained in the mineral, without causing phosphate leaching. To this end, chrysotile (Mg3SiO5(OH)4) was treated with phosphoric acid (H3PO4) in a molar ratio of 1:3 in an aqueous medium at 85 °C until the solvent evaporated, resulting in two different solid compounds, which were prepared in a similar manner. The first compound (cri/H3PO4 1:3)1, was obtained by rinsing and then heat-treating it at 150 °C for 6 h, while the second one, (cri/H3PO4 1:3)2, was rinsed after the heat treatment. Compound (cri/H3PO4 1:3)1 underwent partial leaching, while compound (cri/H3PO4 1:3)2 showed a mass increase of 48%, with the formation of crystalline magnesium pyrophosphate mixed with amorphous SiO2. The latter compound adsorbed N-NH3 at pH 10, following the pseudo-first-order model (activation energy = 8329 ± 1696 J mol-1). Equilibrium experiments, which were performed following Hill's sigmoidal type S2 isotherm model, indicated that the adsorption phenomenon was governed by two processes, i.e., complexation up to the inflection point (KH between 10.0 mg L-1 at 40 °C and 13.6 mg L-1 at 25 °C) followed by adsorption. The qmax varied from 18.0 to 19.6 mgN g-1 and the adsorbent was reusable, maintaining its initial adsorbent capacity during its first reuse. This material, which was tested on real effluents, presented a N-NH3 removal rate similar to that shown by the test solutions. The treatment of chrysotile with H3PO4 conducts it to a composite that adsorbs ammoniacal nitrogen at pH 10 and it is reusable maintaining the adsorption capacity.

Ferromagnetic-like behavior of Co doped TiO2 flexible thin films fabricated via co-sputtering for spintronic applications.

TiO2:Co thin films on ITO (Indium-tin-oxide)/PET (Poly Ethylene Terephthalate) flexible and glass substrates were fabricated via DC magnetron co-sputtering at room temperature. The samples deposited on glass substrates were subjected to annealing processes at 473 K for 2 h to improve the crystallization of the material. Both TiO2:Co/ITO/PET and TiO2:Co/glass thin films exhibited excellent optical properties with more than 80% transmission in the visible region. An increase on ITO/PET surface temperature was detected during the synthesis of the samples; this variation in the ITO substrate ( ∼ 2 K) was associated to impact energetic of ion or atoms bombarded during the deposition process. X-ray diffraction measurements evidenced local phases to growth on the flexible substrate; the random distributions of Cobalt crystals into the rutile and anatase phases were associated to a crystalline lattice embedded with magnetic ions. A configuration of small grains and absence of cluster formation on the surface of thin films was observed through SEM and AFM measurements. From this topographic study and MFM measurements evidenced that surface grains were not constituted magnetic domains formation in the thin films. The ferromagnetic-like behavior was observed in a magnetization as function of field measurement by PPMS. M vs H curves at room temperature for TiO2:Co/ITO/PET thin films, showed the hysteresis loop. The dipolar interaction between Cobalt ions without formation of domains were correlated to the magnetic behavior in the material, as the doping concentration is lower than 12%.

"Self arranged Cactis" as new goethite morphology from the natural corrosion process of SAE 1020 carbon steel.

A new morphology of goethite aggregates (α-FeOOH) obtained through the natural corrosion process of 1020 carbon steel parts exposed to weathering was found. Micrographies obtained by SEM reveal micro and nanostructures with forms of nanosquares, microparticles, nanowires inside microparticles and the unpublished structure of "Self arranged Cactis", all varying between 115 nm and 8 µm. The molecular structure of goethite was characterized by FTIR and elemental analysis of EDX converged with the obtained data. The average corrosion rate for 1020 carbon steel in the weathering was 1.7592 mpy. The data obtained in this work will contribute to the understanding of the corrosion process of 1020 carbon steel, one of the most used in civil construction, as well as in material sciences, where iron oxides are widely used in metallurgy, catalysis and adsorption, and the domain of morphology is fundamental for each application.

Kinetic triplet of Colombian sawmill wastes using thermogravimetric analysis.

The potential of sawmill wastes as a raw material in pyrolysis process is presented in this study. Non-isothermal thermogravimetric analysis (TGA and DTG) and isoconversional methods were employed to determine triplet kinetic (activation energy, reaction model and pre-exponential factor). Through TGA and DTG, the conversion degree is described as a function of temperature for five heating rates (10, 20, 30, 40 and 50 o C/min) and four model-free methods (Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Friedman, and Vyazovkin) with temperatures ranging from 25 to 1000 ° C were employed. Isoconversional lines were built for every method at different isoconversional degrees α ∈ [ 0,1 ] . The activation energy E was found as a function of α in the interval χ I I = [ 0.2 , 0.7 ] where each isoconversional methods were in agreement and the estimated error was sufficiently small. Findings show the same activation energy profile independently of the isoconversional method. In particular the total variation of E in χ I I was as follows: 209.909-228.238 kJ/mol (FWO); 211.235-229.277 kJ/mol (KAS); 223.050-188.512 kJ/mol (Friedman), and 211.449 kJ/mol-229.512 kJ/mol (Vyazovkin). The reaction model of the process in χ I I matched with a two-dimensional diffusion ( D 2 ) by using a master-plot analysis. The calculated and reported parameters are fundamental information for the pyrolysis reactor design using Sawmill wastes as feedstock.

Quantitative evaluation of the surface stability and morphological changes of Cu2O particles.

Cu2O low-index surfaces periodic models have been simulated based on density functional theory. The calculated surfaces energies allowed estimating the morphology by means of the Wulff theorem as well as the investigation of possible paths of morphological changes. Therefore, systematic morphology diagrams and change paths according to the energy modulation in relation to the surfaces stabilizations were elaborated. The applicability of this strategy was exemplified by comparing the obtained results with experimental available data from the literature. The morphology diagrams with the quantitative energetic point of view can be used as a guide to support experimental works in order to understand the relation between surface interactions and crystal growth.

Effect of extrapallial protein of Mytilus californianus on the process of in vitro biomineralization of chitosan scaffolds.

Biomineralization is the process by which diverse organisms have the capacity to create heterogeneous accumulations, derived from organic and inorganic compounds that induce the process of mineral formation. An example of this can be seen an extrapallial protein (EP) of Mytilus californianus, which is responsible for carrying out the biomineralization process. In order to determine their ability to perform the biomineralization process, EP protein was absorbed and mixed in chitosan scaffolds which were tested in simulated physiological fluid. The materials were analyzed by FTIR spectroscopy, field emission scanning electron microscopy-energy-dispersive electron X-ray spectroscopy andX-ray diffraction. Results confirmed that the EP protein stimulates the rapid growth of biological apatite on the chitosan scaffolds. The mixing method favored more the apatite growth as well as the formation of second nucleation sites than the immersion method.

MS2 coliphage inactivation by Al/Fe PILC-activated Catalytic Wet Peroxide Oxidation: multiresponse statistical optimization.

The optimization of the Catalytic Wet Peroxide Oxidation (CWPO) assisted by an Al/Fe-pillared clay (Al/Fe-PILC) was assessed in the inactivation of the MS2 coliphage in the presence of a synthetic surrogate of natural organic matter (NOM). The simultaneous effect of two experimental factors (i) H2O2 dose - (H2O2)d (3.00-25.50 % of the H2O2 theoretically required for full mineralization) and (ii) catalyst concentration (0.33-2.60 g/L), and four non-controllable variables (covariates) (a) circumneutral pH (6.00-9.00), (b) temperature (5.00-25.0 °C), (c) synthetic NOM concentration (2.0-20.0 mg C/L) and (d) MS2 titer (104, 105 and 106 PFU/mL) was investigated by Response Surface Methodology (RSM). Every response was modeled and maximized: (1) MS2 inactivation, (2) fraction of reacted H2O2, (3) decolourization and (4) NOM mineralization. Multi-response optimization via desirability function based on responses (1) to (3) achieved excellent fitting (0.94 out of 1.0) and following set of optimal experimental conditions: 0.33 g Al/Fe-PILC/L, 3.36 % (H2O2)d â€‹(Feactive/H2O2) = 0.46, giving rise to 92.9 % of MS2 inactivation and 100 % of reacted H2O2 at pH 7.07, 25.0 +/- 0.1 °C, 16.06 mg C/L as starting NOM concentration, and MS2 titer of 106 PFU/mL after just 70 min â€‹of reaction.

Sulfonated and gamma-irradiated waste expanded polystyrene with iron oxide nanoparticles, for removal of indigo carmine dye in textile wastewater.

In this work, waste expanded polystyrene (WEPS) was irradiated with gamma rays, ranging doses from 100 kGy to 1,000 kGy. After irradiation, the WEPS had decrease on its glass transition temperature (Tg), as consequence of the scissions of its polymer chains. Then, the irradiated WEPS was sulfonated, and its degree of sulfonation (DS) was measured. The highest DS value, 46.6%, was obtained for an irradiation dose of 200 kGy. The sulfonated and irradiated polystyrene (denominated as iS-WEPS), was used as a support of iron oxide nanoparticles. Such composite system was denominated (FeO-NPs + iS-WEPS). The results show nanoparticle sizes of 31.5 nm containing 21.97% iron oxide. The composites followed a pseudo-second order model, with a maximum adsorption capacity of 20 mg/g, and an equilibrium time of 30 min, according to the Langmuir model. Moreover, the optimal conditions followed by the Fenton process were: pH = 3.2, H2O2 concentration = 0.32 mM/L, composite concentration (FeO-NPs + iS-WEPS) = 2 g/L, and a reaction time 20 min. Finally, 99% removal of indigo carmine dye was achieved, and a reduction of 83% of COD in textile wastewater.

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.

Thermodynamic study of adsorption of nickel ions onto carbon aerogels.

In this work, 8 samples of carbon aerogels with different ratios of catalyst versus resorcinol (R/C) from 25 to 1500 were used. The textural properties were evaluated from N2 adsorption isotherms in 77 K, as well as the chemical ones, where the surface chemistry was evaluated through the Boehm titrations. The results were analyzed and related to the adsorption of the nickel (II) ion from aqueous solution. The experimental results show that the aerogel samples can be divided into two series with different properties: Series I, mainly microporous (low ratio R/C) and Series II (high ratio R/C) mainly microporous but with a contribution of mesoporosity. The specific surface area varied between 64 and 990 m2 g-1. The experimental results show that prepared aerogels have an adequate adsorption capacity towards nickel (II) ions. The behavior of the kinetics of Ni(II) adsorption on carbon aerogels adjusts in a better way the kinetic model of pseudo-second order since it is the one that presents the value of the highest R2 correlation coefficient. The calorimetric data shows that the greater the area developed in carbons aerogels the enthalpy increases.

Biopolymeric pellets of polyvinyl alcohol and alginate for the encapsulation of Ib-M6 peptide and its antimicrobial activity against E. coli.

The encapsulation of Ib-M6 antibacterial peptide in pellets of polyvinyl alcohol (PVA) and polyvinyl alcohol-alginate (PVA-Alg) matrices was carried out in order to explore its controlled release and activity against Escherichia coli K-12. The pellets were obtained by combined ice segregation induced self-assembly (ISISA) and freezing-thawing methods and their microstructure was studied by scanning electron microscopy. Bromothymol blue was used as a model compound to study the transport mechanisms and release from pellets. The results show that there is a significant effect of the total concentration of PVA precursor solutions, the mass ratio of PVA of different molecular weights and the addition of alginate on the microstructure and transport properties of pellets. The antibacterial activity of Ib-M6 against Escherichia coli K-12 was not affected by the encapsulation in PVA pellets. However, the release of Ib-M6 from PVA-Alg pellets was not possible, probably due to the electrostatic interaction of positively charged Ib-M6 and negatively alginate structure. Nonetheless, the controlled release of Ib-M6 from polymeric matrices can be fitting by modifying parameters such as the concentration and type of polymer precursors.

Phosphorus as a promoter of a nickel catalyst to obtain 1-phenylethanol from chemoselective hydrogenation of acetophenone.

Two catalysts were prepared using monodisperse pre-synthetized nanoparticles of metallic nickel and nickel phosphides with the same average diameter. Both nanoparticles species were deposited on the same support: mesoporous silica nano-spheres of MCM-41. This support is suitable to inhibit agglomeration and sintering processes during preparation steps. Therefore, two supported and activated catalysts with the same average nanoparticles diameter were obtained. They differ only in the nature of the active species: metallic nickel and nickel phosphides. The effect of the presence of a second element (phosphorus), more electronegative than nickel, on the activity and selectivity in the chemoselective hydrogenation of acetophenone was studied. The reaction conditions were: H2 pressure of 1 MPa, 80 °C using n-heptane as solvent. With the aim to understand the catalytic results, nanoparticles, support and catalysts were carefully characterized by X-ray diffraction, diffuse light scattering, transmission electron microcopy, high resolution transmission electron microcopy, selected area electron diffraction, scanning electron microcopy, Fourier transformer infrared spectroscopy, N2 adsorption at -196 °C, atomic absorption, H2 and CO chemisorption and volumetric oxidation. Considering these results and geometric and electronic characteristics of the surface of both active species, a change in the adsorption intermediate state of acetophenone in presence of phosphorus is proposed to explain the hydrogenation chemoselectivity of nickel phospides.