Electrochemical Detection of Glyphosate in Surface Water Samples Based on Modified Screen-Printed Electrodes.

This study addresses the necessity to monitor the presence of glyphosate (Gly) in waters, highlighting the need for on-site detection of Gly by using electrochemical sensors in environmental and agricultural monitoring programs. Two approaches were employed: (1) modification with graphene decorated with gold nanoparticles (AuNPs-Gr) and dispersed in either dimethylformamide (DMF) or a solution containing Nafion and isopropanol (NAF), and (2) molecularly imprinted polymers (MIPs) based on polypyrrole (PPy) deposited on gold SPEs (AuSPE). Electrochemical characterization revealed that sensors made of AuNPs-Gr/SPCE exhibited enhanced conductivity, larger active area, and improved charge transfer kinetics compared to unmodified SPEs and SPEs modified with graphene alone. However, the indirect detection mechanism of Gly via complex formation with metallic cations in AuNPs-Gr-based sensors introduces complexities and compromises sensitivity and selectivity. In contrast, MIPPy/AuSPE sensors demonstrated superior performance, offering enhanced reliability and sensitivity for Gly analysis. The MIPPy/AuSPE sensor allowed the detection of Gly concentrations as low as 5 ng/L, with excellent selectivity and reproducibility. Moreover, testing in real surface water samples from the Olt River in Romania showed recovery rates ranging from 90% to 99%, highlighting the effectiveness of the detection method. Future perspectives include expanding the investigation to monitor Gly decomposition in aquatic environments over time, providing insights into the decomposition's long-term effects on water quality and ecosystem health, and modifying regulatory measures and agricultural practices for mitigating its impact. This research contributes to the development of robust and reliable electrochemical sensors for on-site monitoring of Glyphosate in environmental and agricultural settings.

NASICON Membrane with High Ionic Conductivity Synthesized by High-Temperature Solid-State Reaction.

In the present work, we studied the impact of excess Na addition on the structure of the standard NASICON ion conductor along with Na ion transport mechanisms. In this sense, NASICON ceramic membranes (NZSP) were prepared by a simple chemical synthesis method, the solid state reaction (SSR), using an excess of 5% Na (Na3.15Zr2Si2PO12) and an excess of 10% Na (Na3.3Zr2Si2PO12), in order to improve the conduction properties of the ceramic membrane. The characterization of the NZSP nanoparticles was performed by measuring the particle size by dynamic light scattering (DLS), the morphology of the NASICON samples pre-sintered at 1100 °C was analyzed by the SEM method (scanning electron microscope), and X-ray diffraction (XRD) analysis was used to investigate the crystal structure of samples, while the surface area was measured using the BET technique. The electrical properties (i.e., ionic conductivity) were evaluated by impedance spectroscopic methods at room temperature (RT). Following the experiments for NASICON membranes without Na excess, with 5% Na excess, and with 10% Na excess synthesized at different pressing forces and sintering temperatures, it was found that membranes with a 10% Na excess, sintered at 1175 °C for 10 h, presented a good ionic conductivity (4.72 × 10-4 S/cm).

Preparation of Copper-Based Catalysts for Obtaining Methanol by the Chemical Impregnation Method.

This paper presents the preparation of heterogeneous catalysts for the direct hydrogenation process of CO2 to methanol. The development of the modern chemical industry is inextricably linked to the use of catalytic processes. As a result, currently over 80% of new technologies introduced in the chemical industry incorporate catalytic processes. Since the basic factor of catalytic processes is the catalysts, the studies for the deepening of the knowledge regarding the nature of the action of the catalysts, for the development of new catalysts and catalytic systems, as well as for their improvement, represent a research priority of a fundamental or applied nature. The Cu/ZnO/Al2O3 catalyst for the synthesis of green methanol, using precursors of an inorganic (copper nitrate, denoted by Cu/ZnO/Al2O3-1) and organic (copper acetate, denoted by Cu/ZnO/Al2O3-2) nature, are obtained by chemical impregnation that includes two stages: preparation and one of calcination. The preparation methods and conditions, as well as the physico-chemical properties of the catalyst precursor, play a major role in the behavior of the catalysts. The prepared catalysts were characterized using atomic adsorption analysis, scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, specific surface area and pore size analyses, adsorption, and the chemisorption of vapor (BET).

Platinum-Functionalized Graphene Oxide: One-Pot Synthesis and Application as an Electrocatalyst.

This paper presents the preparation of platinum on a reduced graphene oxide matrix (PtrGO) using the microwave-assisted method with three different pH solutions. The platinum concentration determined by energy-dispersive X-ray analysis (EDX) was 4.32 (weight%), 2.16 (weight %) and 5.70 (weight%), corresponding to pH 3.3, 11.7 and 7.2, respectively. Pt functionalization of reduced graphene oxide (rGO) decreased the rGO specific surface, as shown by Brunauer, Emmett and Teller (BET) analysis. An XRD spectrum of platinum-decorated reduced graphene oxide (rGO) showed the presence of the associated phases of rGO and centered cubic platinum peaks. An oxygen reduction reaction (ORR) electrochemical characterization performed using the rotating disk electrode (RDE) method showed that in PtGO1 synthetized in an acidic environment, with 4.32 Pt (weight%) determined by EDX, platinum is much more dispersed, which explains its better electrochemical oxygen reduction reaction performance. Koutecky-Levich (K-L) plots calculated at different potentials prove a good linear relationship. Electron transfer numbers (n) determined from the K-L plots are between 3.1 and 3.8, which confirms that the ORR for all the samples can be regarded as first-order reaction kinetics of O2 concentration formed on the Pt surface during ORR.

Eco-Friendly Alternative Disposal through the Pyrolysis Process of Meat and Bone Meal.

The capitalization of agri-food waste is essential for the sustainability of a circular economy. This work focuses on a solution to eliminate such waste, meat and bone meal (MBM), which is produced in large quantities by the food industry and is prohibited for use as animal feed under the European directives. Therefore, with the focus of converting waste to energy, the catalytic pyrolysis of MBM in the presence of mesoporous silica nanocatalysts (SBA-3 and SBA-16 materials and metallic derivates) was investigated in a home-made reactor for the production of renewable energy. The mesoporous silica materials were synthesized using relatively simple methods and then characterized in order to determine their morpho-structural characteristics. The MBM pyrolysis behavior under different experimental conditions was examined in detail, both in the presence and absence of the new catalysts. The resulting MBM-based pyrolysis products, MBMPYOILs and MBMPYGASs, were also assessed as potential alternative fuels, highlighting comparable energy values to conventional fuels. The outcomes of this investigation offer a potential pathway to the clean production of gas and oil, thus promoting the high-grade utilization of MBM waste.

Iodine-Doped Graphene Oxide: Fast Single-Stage Synthesis and Application as Electrocatalyst.

Iodine-doped graphene oxide is attracting great attention as fuel cell (FC) electrocatalysts with a high activity for the oxygen reduction reaction (ORR). However, most of the reported preparation techniques for iodine-doped graphene (I/rGO) could be transposed into practice as multiple step procedures, a significant disadvantage for scale-up applications. Herein, we describe an effective, eco-friendly, and fast technique for synthesis by a microwave-tuned one-stage technique. Structural and morphological characterizations evidenced the obtaining of nanocomposite sheets, with iodine bonded in the graphene matrix. The ORR performance of I/rGO was electrochemically investigated and the enhancement of the cathodic peak was noted. Based on the noteworthy electrochemical properties for ORR activity, the prepared I/rGO can be considered an encouraging alternative for a more economical electrode for fuel cell fabrication and commercialization. In this perspective, the iodine-based catalysts synthesis can be considered a step forward for the metal-free electrocatalysts development for the oxygen reduction reaction in fuel cells.

Influence of Convective and Vacuum-Type Drying on Quality, Microstructural, Antioxidant and Thermal Properties of Pretreated Boletus edulis Mushrooms.

Freshly harvested Boletus edulis mushrooms are subjected to rapid loss of quality due to the high moisture content and enzymatic activity. Drying time, quality characteristics, microstructural and thermal properties were studied in mushrooms ground to puree subjected to hot air drying (HAD), freeze drying (FD) and centrifugal vacuum drying (CVD). The influence of hot water blanching and UV-C pretreatments was additionally investigated. The rehydration ability of mushroom powders was improved by FD, especially without pretreatment or combined to UV-C exposure. The HAD and CVD, with no pretreatment or combined to UV-C, ensured good preservation of phenolics and antioxidant activity of dried mushrooms. The total difference in color of mushroom pigments extracted in acetone was lower in samples dried by CVD and higher in ones by FD. Blanching before HAD produced whiter product probably due to the reduced polyphenoloxidase activity. Scanning Electron Microscopy (SEM) analysis showed fewer physical changes in FD-samples. Heat-induced structural changes were noticed by Differential Scanning Calorimetry (DSC), Thermogravimetry (TG) and Derivative Thermogravimetry (DTG) analysis, in particular of biopolymers, confirmed by ATR-FTIR analysis. Based on our complex approach, the UV pretreatment of mushrooms could be a better alternative to water blanching. Centrifugal vacuum emerged as a new efficient drying method in terms of bioactive compounds, color and thermal stability, while FD led to better rehydration ability and microstructure.

Dehalogenation of α-hexachlorocyclohexane by iron sulfide nanoparticles: Study of reaction mechanism with stable carbon isotopes and pH variations.

The biodegradation of hexachlorocyclohexanes (HCHs) is known to be accompanied by isotope fractionation of carbon (13C/12C), but no systematic studies were performed on abiotic degradation of HCH isomers by iron (II) minerals. In this study, we explored the carbon isotope fractionation of α-HCH during dechlorination by FeS nanoparticles at different pH values. The results of three different experiments showed that the apparent rate constants during dehalogenation of α-HCH by FeS increased with pH. The lowest apparent rate constant value α-HCH during dehalogenation by FeS was 0.009 d-1 at pH value of 2.4, while the highest was 1.098 d-1 at pH 11.8. α-HCH was completely dechlorinated by FeS only at pH values 9.9 and 11.8, while the corresponding apparent rate constants were 0.253 d-1 and 1.098 d-1, respectively. Regardless of the pH used, the 1,2,4-trichlorobenzene (1,2,4-TCB), 1,2-dichlorobenzene (1,2-DCB), and benzene were the dominant degradation products of α-HCH. An enrichment factor (εC) of -4.7 ± 1.3‰ was obtained for α-HCH using Rayleigh model, which is equivalent to an apparent kinetic isotope effect (AKIEC) value of 1.029 ± 0.008 for dehydrohalogenation, and of 1.014 ± 0.004 for dihaloelimination, respectively. The magnitude of isotope fractionation from this study suggests that abiotic isotope fractionation by FeS must be taken into account in anoxic sediments and aquifers contaminated with HCH isomers, when high concentrations of FeS are present in the above-mentioned anoxic environments.