RESUMO

Cu2ZnSnSe4 (CZTSe) nanoparticles (NPs) were successfully synthesized via a solvothermal method. Their structural, compositional, morphological, optoelectronic, and electrochemical properties have been characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Field-emission scanning electron microscopy (FE-SEM), transmission electron microscope (TEM), UV-vis absorption spectroscopy, and electrochemical impedance spectroscopy (EIS) techniques. Porosimetry and specific surface area in terms of the Brunauer-Emmett-Teller (BET) technique have also been studied. XRD indicates the formation of a polycrystalline kesterite CZTSe phase. Raman peaks at 173 and 190 cm-1 confirm the formation of a pure phase. TEM micrographs revealed the presence of nanoparticles with average sizes of ~90 nm. A BET surface area of 7 m2/g was determined. The CZTSe NPs showed a bandgap of 1.0 eV and a p-type semiconducting behavior. As a proof of concept, for the first time, the CZTSe NPs have been used as a visible-light-driven photocatalyst to Congo red (CR) azo dye degradation. The nanophotocatalyst material under simulated sunlight results in almost complete degradation (96%) of CR dye after 70 min, following a pseudo-second-order kinetic model (rate constant of 0.334 min-1). The prepared CZTSe was reusable and can be repeatedly used to remove CR dye from aqueous solutions.

RESUMO

A solvothermal synthesis of ultrasmall cerium oxide nanoparticles (USCeOxNPs) with an average size of 0.73 ± 0.07 nm using deep eutectic solvent (DES) as a stabilizing medium at a temperature of 90 ºC is reported. Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) were used to morphologically characterize the USCeOxNPs. These revealed approximately spherical shapes with emission lines characteristic of cerium. Selected area electron diffraction (SAED) was used to determine the crystalline structure of the cerium oxide nanoparticles (CeO2NPs), revealing the presence of crystalline cubic structures. The USCeOxNPs-DES/CB film was characterized by scanning electron microscopy (SEM), which demonstrated the spherical characteristic of CB with layers slightly covered by DES residues. DES was characterized by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR), indicating its formation through hydrogen bonds between the precursors. An electrochemical sensor for dopamine (DA) determination in biological fluids was developed using the USCeOxNPs together with carbon black (CB). An enhanced current response was observed on DA voltammetric determination, and this can be attributed to the USCeOxNPs. This sensor displayed linear responses for DA in the range 5.0 × 10-7 mol L-1 to 3.2 × 10-4 mol L-1, with a limit of detection of 80 nmol L-1. Besides detectability, excellent performances were verified for repeatability and anti-interference. The sensor based on USCeOxNPs synthesized in DES in a simpler and environmentally friendly way was successfully applied to determine DA in biological matrix.

Assuntos

Cério , Dopamina , Técnicas Eletroquímicas , Cério/química , Dopamina/análise , Dopamina/sangue , Técnicas Eletroquímicas/métodos , Humanos , Solventes Eutéticos Profundos/química , Nanopartículas/química , Limite de Detecção , Nanopartículas Metálicas/química , Tamanho da Partícula

RESUMO

Rare earth bisphthalocyanines (MPc2) are of particular interest because of their behavior as single-molecular magnets, which makes them suitable for applications in molecular spintronics, high-density data storage and quantum computation. Nevertheless, MPc2 are not commercially available, and the synthesis routes are mainly focused on obtaining substituted phthalocyanines. Two preparation routes depend on the precursor: synthesis from phthalonitrile (PN) and the metalation of free or dilithium phthalocyanine (H2Pc and Li2Pc). In both options, byproducts such as free-base phthalocyanine and in the first route additional PN oligomers are generated, which influence the MPc2 yield. There are three preparation methods for these routes: heating, microwave radiation and reflux. In this research, solvothermal synthesis was applied as a new approach to prepare yttrium, lanthanum, gadolinium and terbium unsubstituted bisphthalocyanines using Li2Pc and the rare earth(III) acetylacetonates. Purification by sublimation gave high product yields compared to those reported, namely 68% for YPc2, 43% for LaPc2, 63% for GdPc2 and 62% for TbPc2, without any detectable presence of H2Pc. Characterization by infrared, Raman, ultraviolet-visible and X-ray photoelectron spectroscopy as well as elemental analysis revealed the main featuresof the four bisphthalocyanines, indicating the success of the synthesis of the complexes.

RESUMO

Despite the structural and electrochemical advantages of LiFePO4 (LFP) as a cathode material, the solid-state reaction commonly used as a method to produce it at the industrial level has known disadvantages associated with high energy and fossil fuel consumption. On the other hand, solution-based synthesis methods present a more efficient way to produce LFP and have advantages such as controlled crystal growth, homogeneous morphology, and better control of pollutant emissions because the reaction occurs within a closed system. From an environmental point of view, different impacts associated with each synthesis method have not been studied extensively. The use of less polluting precursors during synthesis, as well as efficient use of energy and water, can provide new insights into the advantages of each cathode material for more environmentally friendly batteries. In this work, a solvothermal method is compared to a solid-state synthesis method commonly used to elaborate LFPs at the commercial level in order to evaluate differences in the environmental impacts of both processes. The solvothermal method used was developed considering the reutilization of solvent, water reflux, and a low thermal treatment to reduce pollutant emissions. As a result, a single high crystallinity olivine phase LFP was successfully synthesized. The use of ethylene glycol (EG) as a reaction medium enabled the formation of crystalline LFP at a low temperature (600 °C) with a nano-plate-like shape. The developed synthesis method was evaluated using life cycle analysis (LCA) to compare its environmental impact against the conventional production method. LCA demonstrated that the alternative green synthesis process represents 60% and 45% of the Resource Depletion impact category (water and fossil fuels, respectively) of the conventional method. At the same time, in the Climate change and Particular matter impact categories, the values correspond to 49 and 38% of the conventional method, respectively.

RESUMO

Organic-inorganic hybrid materials have emerged as a class of novel materials over the last two decades, as they combine functional organic components and inorganic building blocks into unique materials through various chemical or physical interactions. In the present work, the importance of the use of ethylenediamine in sulfided materials applied to photocatalytic processes in the H2 production is demonstrated. The ZnS/ZnO heterojunction was prepared by the solvothermal synthesis in the presence and absence of ethylenediamine. The photocatalytic behavior showed that the addition of ethylenediamine increases the photocatalytic efficiency up to eight times compared to the photocatalyst without the organic agent. The materials were characterized by X-ray diffraction, scanning electron microscopy, infrared and UV-visible spectroscopies of solids, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and photoelectrochemical characterization. The ethylenediamine plays a double role: to stabilize the cubic phase of zinc sulfide and to act as a promoter molecule of charge transfer on the surface of ZnS/ZnO/en heterojunction, slowing down the rate of recombination of the electron-hole pair, which is reflected in a decrease in the resistance to transfer of charge carriers, improving the H2 production rate until 1564 µmol h-1 g-1.

RESUMO

The synthesis of anatase TiO2 nanoparticles with controlled morphology and increased {001} facets exposed without the presence of fluorine-derived substances is a challenge. Herein, we report a highly effective approach to fabricate anatase TiO2 nanoplates with exposed {001} facets and their exploitation as robust photocatalytic materials for dye remediation. These materials were synthesized under controlled hydrolysis and condensation reactions, using titanium (IV) n-butoxide in an ethanolic solution, with acetic and sulfuric acids, by a solvothermal method at 190 °C with or without the presence of the non-ionic surfactant Triton® X-100 and then characterized. During TiO2 crystal synthesis, the effect of a non-ionic surfactant on the TiO2 particle growth was investigated. Our results demonstrate that the proposed method can synthesize pure and crystalline anatase TiO2 square nanoplates that form nanostructured spheres with high surface area, uniformly sized mesopores, and exposed {001} facets. The presence of non-ionic surfactant increased the exposed {001} facets percentage of the formed nanoplates from 69 to 80%, decreased the crystallite thickness, but unaffected its crystalline phase and band gap energy. The kinetic constants (Ka e Kb) for the synthesized TiO2 anatase nanoplates are considerably higher than the commercial TiO2 anatase constant (Kc). The synthesized photocatalysts show higher efficiency in the photocatalytic removal of methylene blue (MB) than commercial TiO2 (for t = 120 min).

Assuntos

Azul de Metileno , Titânio , Catálise , Azul de Metileno/química , Tensoativos , Titânio/química

RESUMO

Magnesium oxide nanoparticles (MgO NPs) were obtained by the calcination of precursor microparticles (PM) synthesized by a novel triethylamine-based precipitation method. Scanning electron microscopy (SEM) revealed a mean size of 120 nm for the MgO NPs. The results of the characterizations for MgO NPs support the suggestion that our material has the capacity to attack, and have an antibacterial effect against, Gram-negative and Gram-positive bacteria strains. The ability of the MgO NPs to produce reactive oxygen species (ROS), such as superoxide anion radicals (O2•-) or hydrogen peroxide (H2O2), was demonstrated by the corresponding quantitative assays. The MgO antibacterial activity was evaluated against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria, with minimum inhibitory concentrations (MICs) of 250 and 500 ppm on the microdilution assays, respectively. Structural changes in the bacteria, such as membrane collapse; surface changes, such as vesicular formation; and changes in the longitudinal and horizontal sizes, as well as the circumference, were observed using atomic force microscopy (AFM). The lipidic peroxidation of the bacterial membranes was quantified, and finally, a bactericidal mechanism for the MgO NPs was also proposed.

RESUMO

Industry 4.0 and the Internet of Things have significantly increased the use of sensors and electronic products based on flexible substrates, which require electrical energy for their performance. This electrical energy can be supplied by piezoelectric vibrational energy harvesting (pVEH) devices. These devices can convert energy from ambient mechanical excitations into electrical energy. In order to develop, these devices require piezoelectric films fabricated with a simple and low-cost process. In this work, we synthesize ZnO nanorod film by a solvothermal method and deposit by spraying on ITO (indium-tin-oxide)/PET (polyethylene terephthalate) flexible substrate for a pVEH microdevice. The results of the characterization of the ZnO nanorod film using X-ray diffraction (XRD) confirm the typical reflections for this type of nanomaterial (JCPDS 36-145). Based on transmission electron microscopy (TEM) images, the size of the nanorod film is close to 1380 nm, and the average diameter is 221 ± 67 nm. In addition, the morphological characteristics of the ZnO nanorod film are obtained using atomic force microscopy (AFM) tapping images. The pVEH microdevice has a resonant frequency of 37 Hz, a generated voltage and electrical power of 9.12 V and 6.67 µW, respectively, considering a load resistance of 107.7 kΩ and acceleration of 1.5 g. The ZnO nanorod film may be applied to pVEH microdevices with flexible substrates using a low-cost and easy fabrication process.

RESUMO

Zinc oxide nanoparticles were successfully synthesized under precipitation processes, using ZnSO4·7H2O as a Zn2+ precursor and K2CO3 used as a basic source, and hydrozincite was obtained as an intermediary, which was treated under two procedures; first procedure involved multiple stages to get final precipitated with NaOH, and in the second procedure the hydrozincite was straightforwardly dried at 220 °C. By both processes ZnO structures were obtained, which were turned into nanoparticles by a solvothermal treatment, for four hours in ethylene glycol at 200 °C. The final products for the first procedure was conglomerate of spherical nanoparticles with sizes ranged between 5-10 nm and dispersed ellipsoidal nanoparticles for the second procedure. Apart off the two procedures mentioned above, another synthesis was carried out with the same Zn2+ precursor but now using NaOH, and the solvothermal treatment produced ZnO mixed micro-structures which under ultrasonic cavitation disaggregated on mesoporous ZnO nanoplates of hexagonal shapes with nanopore sizes of approximately 0.35 nm. All ZnOs synthesized were structurally characterized with XRD, TEM and FT-IR techniques, and electronically with UV-Vis absorption and diffuse reflectance spectroscopies.

RESUMO

A solvothermal method was used to prepare zinc ferrite spinel oxide (ZnFe2O4) using ethylene glycol and 1,4 butanediol as solvent diols, and the influence of diols on the physical properties of ZnFe2O4 particles was investigated. The produced particles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption isotherms, and the catalytic activity for the organic pollutant decomposition by heterogeneous photo-Fenton reaction was investigated. Both solvents produced particles with cubic spinel structure. Microporous and mesoporous structures were obtained when ethylene glycol and 1,4 butanediol were used as diols, respectively. A higher pore volume and surface area, as well as a higher catalytic activity for the pollutant degradation were found when 1,4 butanediol was used as solvent.