Co3O4/activated carbon nanocomposites as electrocatalysts for the oxygen evolution reaction.

The Oxygen Evolution Reaction (OER) is crucial in various processes such as hydrogen production via water splitting. Several electrocatalysts, including metal oxides, have been evaluated to enhance the reaction efficiency. Zeolitic Imidazolate Framework-67 (ZIF-67) has been employed as a precursor to produce Co3O4, showing high OER activity. Additionally, the formation of composites with carbon-based materials improves the activity of these materials. Thus, this work focuses on synthesizing ZIF-67 and commercial activated carbon (AC) composites, which were used as precursors to obtain Co3O4/C electrocatalysts by calculating ZIF-67/CX (X = 10, 30, and 50, the mass percentage of AC). The obtained materials were thoroughly characterized by employing X-ray powder diffraction (XRD), confirming the cobalt oxide structure with a sphere-like morphology as observed in the TEM images. The presence of oxygen vacancies was confirmed by infrared spectroscopy and EPR measurements. The electrocatalytic performance in the OER was investigated by linear sweep voltammetry (LSV), which revealed an overpotential of 325 mV at 10 mA cm-2 and a Tafel slope value of 65.32 mV dec-1 for Co3O4/C10, superior in activity to several previously reported studies in the literature and electrochemical stability of up to 8 hours. The reduced value of charge transfer resistance, high double-layer capacitance, and the presence of Co3+ ions justify the superior performance of the Co3O4/C10 electrocatalyst.

Insight into synthesis and characterisation of Ga0.9Fe2.1O4 superparamagnetic NPs for biomedical applications.

A Ga3+-substituted spinel magnetite nanoparticles (NPs) with the formula Ga0.9Fe2.1O4 were synthesized using both the one-pot solvothermal decomposition method (TD) and the microwave-assisted heating method (MW). Stable colloidal solutions were obtained by using triethylene glycol, which served as a NPs stabilizer and as a reaction medium in both methods. A narrow size distribution of NPs, below 10 nm, was achieved through selected nucleation and growth. The composition, structure, morphology, and magnetic properties of the NPs were investigated using FTIR spectroscopy, thermal analysis (TA), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and magnetic measurements. NPs with the expected spinel structure were obtained in the case of the TD method, while the MW method produced, additionally, an important amount of gallium suboxide. The NPs, especially those prepared by TD, have superparamagnetic behavior with 2.02 µB/f.u. at 300 K and 3.06 µB/f.u. at 4.2 K. For the MW sample these values are 0.5 µB/f.u. and 0.6 µB/f.u. at 300 K and 4.2 K, respectively. The MW prepared sample contains a secondary phase and very small NPs which affects both the dimensional distribution and the magnetic behavior of NPs. The NPs were tested in vitro on amniotic mesenchymal stem cells. It was shown that the cellular metabolism is active in the presence of Ga0.9Fe2.1O4 NPs and preserves an active biocompatible cytoskeleton.

Development of Iron-Silicate Composites by Waste Glass and Iron or Steel Powders.

There is growing interest in the opportunities regarding construction and demolition wastes, such as glass and metal powders, for developing a circular economy and their transformation into new materials. This management and recycling of construction and demolition waste offers environmental benefits and conservation of natural resources. In this paper, new magnetic composite materials were prepared by wet chemical synthesis methods using crushed glasses and iron and steel waste powders as raw materials. The prepared iron-silicate composites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, infrared (IR), ultraviolet-visible, and electron paramagnetic resonance (EPR) spectroscopy, and magnetic measurements. The XRD data confirm the formation of varied crystalline phases of the iron ions. The presence of the Fe3O4 crystalline phase was detected in the composites containing the iron waste powders. The inspection of the SEM micrographs revealed slightly better homogeneity for the composite material containing larger amounts of iron waste and heterogeneous morphology with cracks and random crystallinity for the composite doped with steel waste. By doping with different contents of iron or steel waste powder, structural modifications in the silicate network and the formation of new bands in the IR spectra were evidenced. The UV-Vis spectra were characterized by the absorption peaks for both the tetrahedral and octahedral geometries of the Fe3+ ions and the octahedral coordination of the Fe2+ ions with oxygen anions. The EPR data show resonance lines with g ~2, 4.3, and 6.4, corresponding to the Fe3+ ions. Using hysteresis curves, the superparamagnetic properties of the iron-silicate composites were evidenced.

Photoluminescence and Photocatalytic Properties of MWNTs Decorated with Fe-Doped ZnO Nanoparticles.

The present work reports the photoluminescence (PL) and photocatalytic properties of multi-walled carbon nanotubes (MWCNTs) decorated with Fe-doped ZnO nanoparticles. MWCNT:ZnO-Fe nanocomposite samples with weight ratios of 1:3, 1:5 and 1:10 were prepared using a facile synthesis method. The obtained crystalline phases were evidenced by X-ray diffraction (XRD). X-ray Photoelectron spectroscopy (XPS) revealed the presence of both 2+ and 3+ valence states of Fe ions in a ratio of approximately 0.5. The electron paramagnetic resonance EPR spectroscopy sustained the presence of Fe3+ ions in the ZnO lattice and evidenced oxygen vacancies. Transmission electron microscopy (TEM) images showed the attachment and distribution of Fe-doped ZnO nanoparticles along the nanotubes with a star-like shape. All of the samples exhibited absorption in the UV region, and the absorption edge was shifted toward a higher wavelength after the addition of MWCNT component. The photoluminescence emission spectra showed peaks in the UV and visible region. Visible emissions are a result of the presence of defects or impurity states in the material. All of the samples showed photocatalytic activity against the Rhodamine B (RhB) synthetic solution under UV irradiation. The best performance was obtained using the MWCNT:ZnO-Fe(1:5) nanocomposite samples, which exhibited a 96% degradation efficiency. The mechanism of photocatalytic activity was explained based on the reactive oxygen species generated by the nanocomposites under UV irradiation in correlation with the structural and optical information obtained in this study.

Green Synthesized Gold and Silver Nanoparticles Increased Oxidative Stress and Induced Cell Death in Colorectal Adenocarcinoma Cells.

The research investigated the effect of gold (Au-CM) and silver nanoparticles (Ag-CM) phytoreduced with Cornus mas fruit extract (CM) on a human colorectal adenocarcinoma (DLD-1) cell line. The impact of nanoparticles on the viability of DLD-1 tumor cells and normal cells was evaluated. Oxidative stress and cell death mechanisms (annexin/propidium iodide analysis, caspase-3 and caspase-8 levels, p53, BCL-2, BAX, NFkB expressions) as well as proliferation markers (Ki-67, PCNA and MAPK) were evaluated in tumor cells. The nanoparticles were characterized using UV-Vis spectroscopy and transmission electron microscopy (TEM) and by measuring zeta potential, hydrodynamic diameter and polydispersity index (PDI). Energy dispersive X-ray (EDX) and X-ray powder diffraction (XRD) analyses were also performed. The nanoparticles induced apoptosis and necrosis of DLD-1 cells and reduced cell proliferation, especially Ag-CM, while on normal cells, both nanoparticles maintained their viability up to 80%. Ag-CM and Au-CM increased the expressions of p53 and NFkB in parallel with the downregulation of BCL-2 protein and induced the activation of caspase-8, suggesting the involvement of apoptosis in cell death. Lipid peroxidation triggered by Ag-CM was correlated with tumor cell necrosis rate. Both nanoparticles obtained with phytocompounds from the CM extract protected normal cells and induced the death of DLD-1 tumor cells, especially by apoptosis.

Mutual inhibition effect of sulfur compounds in the hydrodesulfurization of thiophene, 2-ethylthiophene and benzothiophene ternary mixture.

The hydrodesulphurization of a model component and equimolar ternary mixture of thiophene, 2-ethylthiophene and benzothiophene over sulphided CoMo/γ-Al2O3 and CoMo/γ-Al2O3-Nb2O5 catalysts were investigated in a fixed bed flow reactor. The catalysts were prepared by incipient wetness impregnation method and characterized by textural characteristics, total acidity and chemical species present on the catalysts surface. The characterization results showed that both CoMo/γ-Al2O3-Nb2O5 and sulphided CoMo/γ-Al2O3 catalysts exhibit a mesoporous structure with cylindrical pores open at both ends, evidenced by the IV type adsorption-desorption isotherm with a H1 hysteresis loop and have an average pore diameter between 3 and 4 nm. The chemical species present on the catalysts surface evaluated by XPS indicated that Co2+ and Mo4+ species are present in the sulfide form on both catalysts surfaces. In addition, there are also found oxidic species arising from incomplete reduction and sulphidation. The presence of niobium oxide in the catalytic support had a positive effect in leading to higher specific surface area (170 m2/g) and total acidity (0.421 meq/g) compared with CoMo/γ-Al2O3 catalyst (140 m2/g and 0.283 meq/g) respectively. The evaluation results from the hydrodesulfurization showed that CoMo/γ-Al2O3-Nb2O5 catalyst had a higher activity in hydrodesulphurization process of thiophene, 2-ethylthiophene and benzothiophene. The CoMo/γ-Al2O3-Nb2O5 catalyst eliminated sulfur from the single component feed (corresponding to 2380 ppm S) and reduced below 10 ppm, for the feed consisting in the equimolar ternary mixture of thiophene, 2-ethylthiophene and benzothiophene (2380 ppm S). The reactivity of thiophen compounds was reduced due to competitive adsorption. It was observed that benzothiophene inhibits the transformation of thiophene and 2-ethylthiophene. A mutual inhibition effect between sulfur compounds was also observed when thiophene, 2-ethylthiophene and benzothiophene were combined and tested over the CoMo/γ-Al2O3 catalyst. The inhibition effect had a lower intensity by introducing Nb2O5 in the catalyst support.

Eco-Friendly Nitrogen-Doped Graphene Preparation and Design for the Oxygen Reduction Reaction.

Four N-doped graphene materials with a nitrogen content ranging from 8.34 to 13.1 wt.% are prepared by the ball milling method. This method represents an eco-friendly mechanochemical process that can be easily adapted for industrial-scale productivity and allows both the exfoliation of graphite and the synthesis of large quantities of functionalized graphene. These materials are characterized by transmission and scanning electron microscopy, thermogravimetry measurements, X-ray powder diffraction, X-ray photoelectron and Raman spectroscopy, and then, are tested towards the oxygen reduction reaction by cyclic voltammetry and rotating disk electrode methods. Their responses towards ORR are analysed in correlation with their properties and use for the best ORR catalyst identification. However, even though the mechanochemical procedure and the characterization techniques are clean and green methods (i.e., water is the only solvent used for these syntheses and investigations), they are time consuming and, generally, a low number of materials can be prepared, characterized and tested. In order to eliminate some of these limitations, the use of regression learner and reverse engineering methods are proposed for facilitating the optimization of the synthesis conditions and the materials' design. Thus, the machine learning algorithms are applied to data containing the synthesis parameters, the results obtained from different characterization techniques and the materials response towards ORR to quickly provide predictions that allow the best synthesis conditions or the best electrocatalysts' identification.

Electrospun Nanosystems Based on PHBV and ZnO for Ecological Food Packaging.

The electrospun nanosystems containing poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and 1 wt% Fe doped ZnO nanoparticles (NPs) (with the content of dopant in the range of 0-1 wt% Fe) deposited onto polylactic acid (PLA) film were prepared for food packaging application. They were investigated by scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), antimicrobial analysis, and X-ray photoelectron spectrometry (XPS) techniques. Migration studies conducted in acetic acid 3% (wt/wt) and ethanol 10% (v/v) food simulants as well as by the use of treated ashes with 3% HNO3 solution reveal that the migration of Zn and Fe falls into the specific limits imposed by the legislation in force. Results indicated that the PLA/PHBV/ZnO:Fex electrospun nanosystems exhibit excellent antibacterial activity against the Pseudomonas aeruginosa (ATCC-27853) due to the generation of a larger amount of perhydroxyl (˙OOH) radicals as assessed using electron paramagnetic resonance (EPR) spectroscopy coupled with a spin trapping method.

Evaluation of CNT-COOH/MnO2/Fe3O4 nanocomposite for ibuprofen and paracetamol removal from aqueous solutions.

The nanocomposite CNT-COOH/MnO2/Fe3O4 was synthesized and characterized by different techniques, namely X-ray diffraction, Fourier-transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller analysis, magnetic measurement, point of zero charge and hydrophobicity index. Analyzes revealed the groups -COOH, MnO2 and Fe3O4 attached to the carbon nanotubes, the acidic character of the obtained nanocomposite and its stability. The surface area for the obtained nanocomposite was 114.2 m2 g-1. The prepared nanocomposite was used for adsorption of ibuprofen and paracetamol from aqueous solution. Isotherm, kinetic and thermodynamic parameters were determined for predicting the ibuprofen and paracetamol adsorption on synthetized nanocomposite. The equilibrium data obtained from adsorption were well represented by Langmuir model and kinetics data were well fitted by the pseudo-second order model. The maximum adsorption capacity obtained for ibuprofen and paracetamol was 103.093 mg g-1, 80.645 mg g-1 respectively. The thermodynamic analysis showed that the adsorption process for both pollutants was spontaneous and endothermic. The synthetized nanocomposite can be a suitable new absorbent for ibuprofen and paracetamol removal from aqueous solutions due to its high adsorbing capacity and it can be separated by an external magnetic field.

Photocatalytic and Electrocatalytic Properties of NGr-ZnO Hybrid Materials.

N-doped graphene-ZnO hybrid materials with different N-doped graphene:ZnO wt% ratios (1:10; 1:20; 1:30) were prepared by a simple and inexpensive sol-gel method. The materials denoted NGr-ZnO-1 (1:10), NGr-ZnO-2 (1:20), and NGr-ZnO-3 (1:30) were investigated with advanced techniques and their morpho-structural, photocatalytic, and electrocatalytic properties were reported. Hence, pure N-doped graphene sample contains flakes with the size ranging from hundreds of nanometers to micrometers. In the case of all NGr-ZnO hybrid materials, the flakes appear heavily decorated with ZnO nanoparticles, having a cauliflower-like morphology. The X-ray powder diffraction (XRD) investigation of N-doped graphene sample revealed that it was formed by a mixture of graphene oxide, few-and multi-layer graphene. After the ZnO nanoparticles were attached to graphene, major diffraction peaks corresponding to crystalline planes of ZnO were seen. The qualitative and quantitative compositions of the samples were further evidenced by X-ray photoelectron spectroscopy (XPS). In addition, UV photoelectron spectroscopy (UPS) spectra allowed the determination of the ionization energy and valence band maxima. The energy band alignment of the hybrid materials was established by combining UV-Vis with UPS results. A high photocatalytic activity of NGr-ZnO samples against rhodamine B solution was observed. The associated reactive oxygen species (ROS) generation was monitored by electron paramagnetic resonance (EPR)-spin trapping technique. In accordance with bands alignment and identification of radical species, the photocatalytic mechanism was elucidated.

Data on the removal of Optilan Blue dye from aqueous media using starch-coated green synthesized magnetite nanoparticles.

In this data article, we present supplementary data related to the research article entitled "Starch-coated green synthesized magnetite nanoparticles for removal of textile dye Optilan Blue from aqueous media" Stan et al., 2019. Data interpretations are included in the related research article Stan et al., 2019. The synthesized starch-coated Fe3O4 nanoparticles (ST-coated Fe3O4 NPs) were analyzed by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) to illustrate the shape and surface coating of nanoparticles. Moreover, the Brunauer-Emmett-Teller (BET) technique was used to evidence starch deposition on magnetite nanoparticles. The obtained nanocomposites were used for adsorption of Optilan Blue (OB) in batch conditions and the optimum agitation speed and point of zero charge (pHpzc) were established. After OB adsorption on ST-coated Fe3O4 NPs, the nanocomposites were analyzed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). The stability of starch coated Fe3O4 NPs in the acidic as well as alkaline pH was also evidenced by FTIR spectroscopy. In addition, to test the stability of ST-coated Fe3O4 NPs, leaching experiments were carried out. The experimental data were compared with isotherm and kinetic models in order to determine the most suitable for fitting.

Photocatalytic activity of SnO2-TiO2 composite nanoparticles modified with PVP.

Interface modified SnO2-TiO2 composite nanoparticles were produced in two stages: first SnO2 nanoparticles were prepared by chemical precipitation in the presence of polyvinylpyrrolidone (PVP) and thermally treated at 500 °C then TiO2 was deposited on top of modified SnO2 and followed by a final annealing. As a consequence SnO2-TiO2 composite nanoparticles get crystallized while PVP is decomposed into monomer units and other attached smaller molecular fragments. TGA coupled with FT-IR spectroscopy confirmed the presence of monomers and other moieties as a result of PVP thermal fragmentation. The crystalline phases and composition of the two oxides were evidenced by X-ray diffraction, HRTEM and XPS. It was found that specific surface area of the composites increases with the increase in the initial amount of PVP. Also, the oxidation potential of the TiO2 shell, as determined by UV photoelectron spectroscopy (UPS), significantly decreases as the PVP quantity increase and further modifies the band alignment between SnO2 and TiO2 components. Additionally, both XPS and UPS spectra as well as EPR investigations indicate the presence of many localized states inside the band gap of TiO2. With a moderate PVP content the combined effects of band alignment, gap localized states and porosity make possible an increased number of reactive oxygen species (ROS) generation thus increasing photocatalytic activity against RhB dye solution under visible irradiation. The photocatalytic mechanism was elucidated based on the identification of radical species involved and in accordance with energy bands alignment, gap states, and porosity. Besides water purification by photocatalysis, SnO2-TiO2, as ROS generating heterostructures may be used in applications like antibacterial and antitumoral, deodorizing, air purifying, self-cleaning, gas sensing, as well as in hydrogen production.

Electrochemical platform based on nitrogen-doped graphene/chitosan nanocomposite for selective Pb2+ detection.

A novel nanocomposite was developed and used for trace determination of Pb2+ cations from aqueous solutions. The nanocomposite was obtained by the association of N-doped graphene (N-Gr) with a biocompatible polymer, namely chitosan (Ch). The characterization of the new nanocomposite material (Ch-N-Gr) was performed using TEM, STEM-EDX, SEM, XRD and XPS techniques. Compared with the bare gold electrode (GE) a remarkable enhancement of the voltammetric response of the modified electrode (Ch-N-Gr/GE) was always observed. Using the Ch-N-Gr/GE, the Pb2+ voltammetric response showed a pair of well defined, quasi-reversible anodic and cathodic peaks, with the peak potentials located at about -0.59 V and -0.69 V, respectively. The calibration curves were obtained over a large linear range, from 10-7 to 10-4 M Pb2+ concentration. Under optimized conditions, the detection limit was found to be 6.64 × 10-8 M. The effect of several interfering species (such as other metallic cations or organic compounds of various concentrations) on the determination of Pb2+ concentration was also studied, and the results proved the selectivity of the proposed modified electrode. The validity and effectiveness of the method was further confirmed by trace determination of Pb2+ in real samples.