Synergistic Catalytic Effect of Ag and MgO Nanoparticles Supported on Defective BN Surface in CO Oxidation Reaction.

Micron-sized supports of catalytically active nanoparticles (NPs) can become a good alternative to nanocarriers if their structure is properly tuned. Here, we show that a combination of simple and easily scalable methods, such as defect engineering and polyol synthesis, makes it possible to obtain Ag and MgO nanoparticles supported on defective hexagonal BN (h-BN) support with high catalytic activity in the CO oxidation reaction. High-temperature annealing in air of Mg-containing (<0.2 at.%) h-BN micropellets led to surface oxidation, the formation of hexagonal-shaped surface defects, and defect-related MgO NPs. The enhanced catalytic activity of Ag/MgO/h-BN materials is attributed to the synergistic effect of h-BN surface defects, ultrafine Ag and MgO NPs anchored at the defect edges, and MgO/Ag heterostructures. In addition, theoretical simulations show a shift in the electron density from metallic Ag towards MgO and the associated decrease in the negative charge of oxygen adsorbed on the Ag surface, which positively affects the catalytic activity of the Ag/MgO/h-BN material.

Electrospun Polycaprolactone/ZnO Nanocomposite Membranes with High Antipathogen Activity.

The spread of bacterial, fungal, and viral diseases by airborne aerosol flows poses a serious threat to human health, so the development of highly effective antibacterial, antifungal and antiviral filters to protect the respiratory system is in great demand. In this study, we developed ZnO-modified polycaprolactone nanofibers (PCL-ZnO) by treating the nanofiber surface with plasma in a gaseous mixture of Ar/CO2/C2H4 followed by the deposition of ZnO nanoparticles (NPs). The structure and chemical composition of the composite fibers were characterized by SEM, TEM, EDX, FTIR, and XPS methods. We demonstrated high material stability. The mats were tested against Gram-positive and Gram-negative pathogenic bacteria and pathogenic fungi and demonstrated high antibacterial and antifungal activity.

A New Insight into the Mechanisms Underlying the Discoloration, Sorption, and Photodegradation of Methylene Blue Solutions with and without BNOx Nanocatalysts.

Methylene blue (MB) is widely used as a test material in photodynamic therapy and photocatalysis. These applications require an accurate determination of the MB concentration as well as the factors affecting the temporal evolution of the MB concentration. Optical absorbance is the most common method used to estimate MB concentration. This paper presents a detailed study of the dependence of the optical absorbance of aqueous methylene blue (MB) solutions in a concentration range of 0.5 to 10 mg·L-1. The nonlinear behavior of optical absorbance as a function of MB concentration is described for the first time. A sharp change in optical absorption is observed in the range of MB concentrations from 3.33 to 4.00 mg·L-1. Based on the analysis of the absorption spectra, it is concluded that this is due to the formation of MB dimers and trimers in the specific concentration range. For the first time, a strong, thermally induced discoloration effect of the MB solution under the influence of visible and sunlight was revealed: the simultaneous illumination and heating of MB solutions from 20 to 80 °C leads to a twofold decrease in the MB concentration in the solution. Exposure to sunlight for 120 min at a temperature of 80 °C led to the discoloration of the MB solution by more than 80%. The thermally induced discoloration of MB solutions should be considered in photocatalytic experiments when tested solutions are not thermally stabilized and heated due to irradiation. We discuss whether MB is a suitable test material for photocatalytic experiments and consider this using the example of a new photocatalytic material-boron oxynitride (BNOx) nanoparticles-with 4.2 and 6.5 at.% of oxygen. It is shown that discoloration is a complex process and includes the following mechanisms: thermally induced MB photodegradation, MB absorption on BNOx NPs, self-sensitizing MB photooxidation, and photocatalytic MB degradation. Careful consideration of all these processes makes it possible to determine the photocatalytic contribution to the discoloration process when using MB as a test material. The photocatalytic activity of BNOx NPs containing 4.2 and 6.5 at.% of oxygen, estimated at ~440 µmol·g-1·h-1. The obtained results are discussed based on the results of DFT calculations considering the effect of MB sorption on its self-sensitizing photooxidation activity. A DFT analysis of the MB sorption capacity with BNOx NPs shows that surface oxygen defects prevent the sorption of MB molecules due to their planar orientation over the BNOx surface. To enhance the sorption capacity, surface oxygen defects should be eliminated.

Mechanical, Structural, and Biological Characteristics of Polylactide/Wollastonite 3D Printed Scaffolds.

The present work aimed to study the synergistic response of bioresorbable polylactide/bioactive wollastonite scaffolds towards mechanical stability, mesenchymal stromal cell colonization, and antibacterial activity in the physiological environment. Wollastonite was synthesized at 800 °C within 2 h by sol-gel combustion method. The surface area was found to be 1.51 m2/g, and Transmission Electron Microscopy (TEM) micrographs indicated the presence of porous structures. Fused deposition modeling was used to prepare 3D-printed polylactide/wollastonite and polylactide/hydroxyapatite scaffolds. Scanning Electron Microscopy (SEM) micrographs confirmed the interconnected porous structure and complex geometry of the scaffolds. The addition of wollastonite decreased the contact angle of the scaffolds. The mechanical testing of scaffolds examined by computational simulation, as well as machine testing, revealed their non-load-bearing capacity. The chemical constituent of the scaffolds was found to influence the attachment response of different cells on their surface. The incorporation of wollastonite effectively reduced live bacterial attachment, whereas the colonization of mesenchymal cells was improved. This observation confirms polylactide/wollastonite scaffold possesses both bactericidal as well as cytocompatible properties. Thus, the risk of peri-implant bacterial film formation can be prevented, and the biological fixation of the scaffold at the defect site can be enhanced by utilizing these composites.

Recent Progress in Fabrication and Application of BN Nanostructures and BN-Based Nanohybrids.

Due to its unique physical, chemical, and mechanical properties, such as a low specific density, large specific surface area, excellent thermal stability, oxidation resistance, low friction, good dispersion stability, enhanced adsorbing capacity, large interlayer shear force, and wide bandgap, hexagonal boron nitride (h-BN) nanostructures are of great interest in many fields. These include, but are not limited to, (i) heterogeneous catalysts, (ii) promising nanocarriers for targeted drug delivery to tumor cells and nanoparticles containing therapeutic agents to fight bacterial and fungal infections, (iii) reinforcing phases in metal, ceramics, and polymer matrix composites, (iv) additives to liquid lubricants, (v) substrates for surface enhanced Raman spectroscopy, (vi) agents for boron neutron capture therapy, (vii) water purifiers, (viii) gas and biological sensors, and (ix) quantum dots, single photon emitters, and heterostructures for electronic, plasmonic, optical, optoelectronic, semiconductor, and magnetic devices. All of these areas are developing rapidly. Thus, the goal of this review is to analyze the critical mass of knowledge and the current state-of-the-art in the field of BN-based nanomaterial fabrication and application based on their amazing properties.

Amorphous MoSxOy/h-BNxOy Nanohybrids: Synthesis and Dye Photodegradation.

Molybdenum sulfide is a very promising catalyst for the photodegradation of organic pollutants in water. Its photocatalytic activity arises from unsaturated sulfur bonds, and it increases with the introduction of structural defects and/or oxygen substitutions. Amorphous molybdenum sulfide (a-MoSxOy) with oxygen substitutions has many active sites, which create favorable conditions for enhanced catalytic activity. Here we present a new approach to the synthesis of a-MoSxOy and demonstrate its high activity in the photodegradation of the dye methylene blue (MB). The MoSxOy was deposited on hexagonal boron oxynitride (h-BNO) nanoflakes by reacting h-BNO, MoCl5, and H2S in dimethylformamide (DMF) at 250 °C. Both X-ray diffraction analysis and high-resolution TEM show the absence of crystalline order in a-MoSxOy. Based on the results of Raman and X-ray photoelectron spectroscopy, as well as analysis by the density functional theory (DFT) method, a chain structure of a-MoSxOy was proposed, consisting of MoS3 clusters with partial substitution of sulfur by oxygen. When a third of the sulfur atoms are replaced with oxygen, the band gap of a-MoSxOy is approximately 1.36 eV, and the valence and conduction bands are 0.74 eV and -0.62 eV, respectively (relative to a standard hydrogen electrode), which satisfies the conditions of photoinduced splitting of water. When illuminated with a mercury lamp, a-MoSxOy/h-BNxOy nanohybrids have a specific mass activity in MB photodegradation of approximately 5.51 mmol g-1 h-1, which is at least four times higher than so far reported values for nonmetal catalysts. The photocatalyst has been shown to be very stable and can be reused.

CO oxidation and organic dyes degradation over graphene-Cu and graphene-CuNi catalysts obtained by solution combustion synthesis.

Graphene and its analogs in combination with metal nanopowders are among the most promising catalysts for various industry valuable processes. The newly obtained solution combustion synthesized graphene-Cu and graphene-CuNi nanocomposites were examined in heterogeneous catalysis of thermal activated CO oxidation and photoactivated degradation of acid telon blue and direct blue dyes. The nanocomposites are characterized by a closely connected solution combustion synthesized graphene-metal structure with a number of graphene layers from 1 to 3 and fine metal grains sizes of 31 nm (Cu) and 14 nm (CuNi). The experimental data showed the obtained graphene-metal nanocomposites are among the most effective catalysts for CO oxidation with a temperature of 100% conversion of 150 °C and 200 °C for Cu and CuNi containing catalysts, respectively. At the same time, both nanopowders were found inactive for dyes degradation.

Ascorbic Acid-Assisted Polyol Synthesis of Iron and Fe/GO, Fe/h-BN Composites for Pb2+ Removal from Wastewaters.

Iron powders and Fe/graphene oxide and Fe/boron nitride composites were synthesized by means of a polyol synthesis method. The effect of NaOH/Fe and ascorbic acid/Fe ratios on the characteristics of synthesized products were evaluated. The samples were characterized by X-ray diffraction, scanning and transmission electron microscopy, low-temperature nitrogen adsorption and Raman-spectroscopy. Ascorbic acid-assisted polyol synthesis resulted in the 10-fold decrease of the iron particles' size and almost 2-fold increase of lead removal efficiency. The deposition of iron on the surface of graphene oxide lead to the formation of small 20-30 nm sized particles as well as bigger 200-300 nm sized particles, while the reduction in presence of boron nitride resulted in the 100-200 nm sized particles. The difference is attributed to the surface state of graphene oxide and boron nitride. Adsorption properties of the obtained materials were studied in the process of Pb2+ ion removal from wastewater.

BN/Ag hybrid nanomaterials with petal-like surfaces as catalysts and antibacterial agents.

BN/Ag hybrid nanomaterials (HNMs) and their possible applications as novel active catalysts and antibacterial agents are investigated. BN/Ag nanoparticle (NP) hybrids were fabricated using two methods: (i) chemical vapour deposition (CVD) of BN NPs in the presence of Ag vapours, and (ii) ultraviolet (UV) decomposition of AgNO3 in a suspension of BN NPs. The hybrid microstructures were studied by high-resolution transmission electron microscopy (HRTEM), high-angular dark field scanning TEM imaging paired with energy dispersion X-ray (EDX) mapping, X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy (FTIR). They were also characterized in terms of thermal stability, Ag+ ion release, catalytic and antibacterial activities. The materials synthesized via UV decomposition of AgNO3 demonstrated a much better catalytic activity in comparison to those prepared using the CVD method. The best catalytic characteristics (100% methanol conversion at 350 °C) were achieved using the UV BN/Ag HNMs without preliminary annealing at 600 °C in an oxidizing atmosphere. Both types of the BN/Ag HNMs possess a profound antibacterial effect against Escherichia coli K-261 bacteria.