Resistive Switching in Bigraphene/Diamane Nanostructures Formed on a La3Ga5SiO14 Substrate Using Electron Beam Irradiation.

Memristors, resistive switching memory devices, play a crucial role in the energy-efficient implementation of artificial intelligence. This study investigates resistive switching behavior in a lateral 2D composite structure composed of bilayer graphene and 2D diamond (diamane) nanostructures formed using electron beam irradiation. The resulting bigraphene/diamane structure exhibits nonlinear charge carrier transport behavior and a significant increase in resistance. It is shown that the resistive switching of the nanostructure is well controlled using bias voltage. The impact of an electrical field on the bonding of diamane-stabilizing functional groups is investigated. By subjecting the lateral bigraphene/diamane/bigraphene nanostructure to a sufficiently strong electric field, the migration of hydrogen ions and/or oxygen-related groups located on one or both sides of the nanostructure can occur. This process leads to the disruption of sp3 carbon bonds, restoring the high conductivity of bigraphene.

Theoretical Analysis of Riboflavin Adsorption on Hexagonal Boron Nitride for Drug Delivery Applications: Unveiling the Influence of Point Defects.

This research delves into the intriguing realm of investigating the stability of vitamin B2 (riboflavin, Rf) on hexagonal boron nitride (h-BN), both in its pristine state and in the presence of vacancy defects, with the aim of harnessing their potential as carriers for drug delivery applications. Employing the density functional theory (DFT), we perform binding energy calculations and analyze the electronic structure of the BN@Rf system to unravel the nature of their interactions. Our comprehensive DFT calculations unequivocally demonstrate the spontaneous physical sorption of the drug onto the h-BN surface, facilitated by the formation of π-π stacking interactions. The adsorption energy spans a range from -1.15 to -4.00 eV per system, emphasizing the robust nature of the BN@Rf bonding. The results show that the HOMO and LUMO of riboflavin are located exactly in the region of the iso-alloxazine rings of riboflavin. This arrangement fosters the formation of π-π stacking between riboflavin and boron nitride, effectively facilitating the transfer of electron density within the BN@Rf system. Furthermore, our investigations reveal the significant impact of vacancy defects within the boron nitride lattice. These vacancies alter the behavior of the structure, prompting riboflavin to metamorphose from an electron donor to an electron acceptor, expanding our understanding of the interplay between boron nitride defects and riboflavin sorption. Therefore, it is imperative to exert meticulous oversight of the structural integrity of h-BN, given that the existence of vacancies may lead to a noticeable change in its adsorption properties. The obtained data could amplify our capacity to conceive and refine drug delivery h-BN-based systems.

The Temperature Dependence of the Hexagonal Boron Nitride Oxidation Resistance, Insights from First-Principle Computations.

In this work, we studied the oxidation stability of h-BN by investigating different variants of its modification by -OH, -O- and -O-O- groups using an atomistic thermodynamics approach. We showed that up to temperatures of ~1700 K, oxygen is deposited on the surface of hexagonal boron nitride without dissociation, in the form of peroxide. Only at higher temperatures, oxygen tends to be incorporated into the lattice of hexagonal boron nitride, except in the presence of defects Nv, when the embedding occurs at all temperatures. Finally, the electronic and magnetic properties of the oxidized h-BN were studied.

Visualization of Swift Ion Tracks in Suspended Local Diamondized Few-Layer Graphene.

In the present study we investigated the nanostructuring processes in locally suspended few-layer graphene (FLG) films by irradiation with high energy ions (Xe, 26-167 MeV). For such an energy range, the main channel of energy transfer to FLG is local, short-term excitation of the electronic subsystem. The irradiation doses used in this study are 1 × 1011-5 × 1012 ion/cm2. The structural transformations in the films were identified by Raman spectroscopy and transmission electron microscopy. Two types of nanostructures formed in the FLG films as a result of irradiation were revealed. At low irradiation doses the nanostructures were formed preferably at a certain distance from the ion track and had the form of 15-35 nm "bunches". We assumed that the internal mechanical stress that arises due to the excited atoms ejection from the central track part creates conditions for the nanodiamond formation near the track periphery. Depending on the energy of the irradiating ions, the local restructuring of films at the periphery of the ion tracks can lead either to the formation of nanodiamonds (ND) or to the formation of AA' (or ABC) stacking. The compressive strain value and pressure at the periphery of the ion track were estimated as ~0.15-0.22% and ~0.8-1.2 GPa, respectively. The main novel results are the first visualization of ion tracks in graphene in the form of diamond or diamond-like rings, the determination of the main condition for the diamond formation (the absence of a substrate in combination with high ion energy), and estimates of the local strain at the track periphery. Generally, we have developed a novel material and have found how to control the film properties by introducing regions similar to quantum dots with the diamond interface in FLG films.

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.

Efficient and Reusable Sorbents Based on Nanostructured BN Coatings for Water Treatment from Antibiotics.

Increasing contamination of wastewater with antibiotics used in agriculture, animal husbandry, and medicine is a serious problem for all living things. To address this important issue, we have developed an efficient platform based on a high specific surface area hexagonal boron nitride (BN) coating formed by numerous nanopetals and nanoneedles. The maximum sorption capacity of 1 × 1 cm2 BN coatings is 502.78 µg/g (tetracycline, TET), 315.75 µg/g (ciprofloxacin, CIP), 400.17 µg/g (amoxicillin, AMOX), and 269.7 µg/g (amphotericin B, AMP), which exceeds the sorption capacity of many known materials. Unlike nanoparticles, BN-coated Si wafers are easy to place in and remove from antibiotic-contaminated aqueous solutions, and are easy to clean. When reusing the adsorbents, 100% efficiency was observed at the same time intervals as in the first cleaning cycle: 7 days (TET) and 14 days (CIP, AMOX, AMP) at 10 µg/mL, 14 days (TET, CIP, and AMOX) and 28 days (AMP) at 50 µg/mL, and 14 days (TET) and 28 days (CIP, AMOX and AMP) at 100 µg/mL. The results obtained showed that TET and CIP are best adsorbed on the surface of BN, so TET was chosen as an example for further theoretical modeling of the sorption process. It was found that adsorption is the main mechanism, and this process is spontaneous and endothermic. This highlights the importance of a high specific surface area for the efficient removal of antibiotics from aqueous solutions.

Diamane Oxide. Two-Dimensional Film with Mixed Coverage and a Variety of Electronic Properties.

Here, we investigate stability of the diamane oxide films and show that various compositions can be realized depending on the precursors, temperature, and pressure. We demonstrate that the commonly used oxygen source in the H2O form requires pressures of GPa order to fabricate the film, which is in full agreement with the experimental data. We show that different types of functional groups can tailor electronic properties of bilayer diamane. Finally, we study electronic property dependence on the film thickness, elucidating its connection with surface states.

Formation of Diamane Nanostructures in Bilayer Graphene on Langasite under Irradiation with a Focused Electron Beam.

In the presented paper, we studied bilayer CVD graphene transferred to a langasite substrate and irradiated with a focused electron beam through a layer of polymethyl methacrylate (PMMA). Changes in the Raman spectra and an increase in the electrical resistance of bigraphene after irradiation indicate a local phase transition associated with graphene diamondization. The results are explained in the framework of the theory of a chemically induced phase transition of bilayer graphene to diamane, which can be associated with the release of hydrogen and oxygen atoms from PMMA and langasite due to the "knock-on" effect, respectively, upon irradiation of the structure with an electron beam. Theoretical calculations of the modified structure of bigraphene on langasite and the experimental evaluation of sp3-hybridized carbon fraction indicate the formation of diamane nanoclusters in the bigraphene irradiated regions. This result can be considered as the first realization of local tunable bilayer graphene diamondization.

Half-Metallic Heusler Alloy/MoS2 Based Magnetic Tunnel Junction.

Integration of half-metallic materials and 2D spacers into vertical magnetoresistive spin valves may pave the way for effective low-power consumption storage and memory technologies. Driven by the recent successful growth of graphene/half-metallic Co2Fe(Ge1/2Ga1/2) (CFGG) heterostructure, here we report a theoretical investigation of magnetic tunnel junction (MTJ) based on the ferromagnetic CFGG Heusler alloy and the MoS2 spacer of different thicknesses. Using ab initio approach, we demonstrate that the inherent ferromagnetism of CFGG is preserved at the interface, while its half-metallicity is recovering within few atomic layers. Ballistic transport in CFGG/MoS2/CFGG MTJ is studied within the nonequilibrium Green's function formalism, and a large magnetoresistance value up to ∼105% is observed. These findings support the idea of effective spintronics devices based on half-metallic Heusler alloys and highly diversified transition metal dichalcogenide family.

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.

The Role of Structural Defects in the Growth of Two-Dimensional Diamond from Graphene.

The presented work is devoted to the study of the formation of the thinnest diamond film (diamane). We investigate the initial stages of diamond nucleation in imperfect bilayer graphene exposed by the deposition of H atoms (chemically induced phase transition). We show that defects serve as nucleation centers, their hydrogenation is energy favorable and depends on the defect type. Hydrogenation of vacancies facilitates the binding of graphene layers, but the impact wanes already at the second coordination sphere. Defects influence of 5|7 is lower but promotes diamondization. The grain boundary role is similar but can lead to the final formation of a diamond film consisting of chemically connected grains with different surfaces. Interestingly, even hexagonal and cubic two-dimensional diamonds can coexist together in the same film, which suggests the possibility of obtaining a new two-dimensional polycrystal unexplored before.

Edges in bilayered h-BN: insights into the atomic structure.

This study is devoted to the study of the edges of bilayered h-BN, whose atomic structure was previously generally unknown. It is shown that the edges tend to connect regardless of the edge cut. A defectless connection can be expected only in the case of a zigzag edge, while in other cases a series of tetragonal and octagonal defects will be formed. This result was obtained by carrying out an analogy between the edge of bilayered h-BN and the interface of monolayer h-BN. Information on the structure and energetics of closed edges allowed us to predict the shape of holes in h-BN, which agreed with the reference experimental data. Finally, it is shown that the closed edges do not create electronic states in the band gap, thus not changing the dielectricity of h-BN.

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.

Electronic properties of graphene oxide: nanoroads towards novel applications.

In this work, we suggest an approach to manipulate the electronic properties of graphene oxide in a controllable manner. We study graphene nanoroads paved inside graphene oxide using density functional calculations. We show that this patterning allows transforming an insulator, graphene oxide, into a semiconductor or metal depending on the orientation of the nanoroads and their magnetic state. As a semiconductor, patterned graphene oxide is characterized by notably low effective masses of charge carriers. Additionally, we demonstrate the possibility to force the transition from a semiconducting to a half-metallic state in a controllable manner, by application of an external electric field. We believe that this remarkable opportunity to combine and control the electronic and magnetic properties of a material within a single sheet of graphene oxide paves the way towards new applications of graphene-oxide-based devices in 2D optoelectronics and spintronics.

Optomechanical Properties of MoSe2 Nanosheets as Revealed by In Situ Transmission Electron Microscopy.

Free-standing few-layered MoSe2 nanosheet stacks optoelectronic signatures are analyzed by using light compatible in situ transmission electron microscopy (TEM) utilizing an optical TEM holder allowing for the simultaneous mechanical deformation, electrical probing and light illumination of a sample. Two types of deformation, namely, (i) bending of nanosheets perpendicular to their basal atomic planes and (ii) edge deformation parallel to the basal atomic planes, lead to two distinctly different optomechanical performances of the nanosheet stacks. The former deformation induces a stable but rather marginal increase in photocurrent, whereas the latter mode is prone to unstable nonsystematic photocurrent value changes and a red-shifted photocurrent spectrum. The experimental results are verified by ab initio calculations using density functional theory (DFT).

Nanohardness from First Principles with Active Learning on Atomic Environments.

We propose a methodology for the calculation of nanohardness by atomistic simulations of nanoindentation. The methodology is enabled by machine-learning interatomic potentials fitted on the fly to quantum-mechanical calculations of local fragments of the large nanoindentation simulation. We test our methodology by calculating nanohardness, as a function of load and crystallographic orientation of the surface, of diamond, AlN, SiC, BC2N, and Si and comparing it to the calibrated values of the macro- and microhardness. The observed agreement between the computational and experimental results from the literature provides evidence that our method has sufficient predictive power to open up the possibility of designing materials with exceptional hardness directly from first principles. It will be especially valuable at the nanoscale where the experimental measurements are difficult, while empirical models fitted to macrohardness are, as a rule, inapplicable.

A DFT study on magnetic interfaces based on half-metallic Co2FeGe1/2Ga1/2 with h-BN and MoSe2 monolayers.

A large variety of recently predicted and synthesized 2D materials significantly broaden the capabilities of magnetic interface design for spintronic applications. Their diverse structural and electronic properties allow fine adjustment of interfacial interactions between the electrode and spacer materials providing robust and effective spin transport. Based on recent experimental results, here we present a theoretical study of novel interfaces formed by a half-metallic Co2FeGe1/2Ga1/2 (CFGG) substrate with h-BN or MoSe2 monolayer on its top. By means of the DFT approach, the structural, magnetic and electronic properties are studied for the Co- and FeGeGa termination of the CFGG surface. The observed large spin polarization in the vicinity of the interface and robust magnetization exhibit the potential of 2D materials/CFGG heterostructures for spintronic applications.

Single-step extraction of small-diameter single-walled carbon nanotubes in the presence of riboflavin.

We propose a novel approach to disperse and extract small-diameter single-walled carbon nanotubes (SWCNTs) using an aqueous solution of riboflavin and Sephacryl gel. The extraction of small-diameter semiconducting SWCNTs was observed, regardless of the initial diameter distribution of the SWCNTs. Dispersion of SWCNTs occurs due to the adsorption of π-conjugated isoalloxazine moieties on the surface of small-diameter nanotubes and interactions between hydroxy groups of ribityl chains with water. During the SWCNT extraction, specific adsorption of riboflavin to SWCNTs leads to the minimization of interactions between the SWCNTs and gel media. Our experimental findings are supported by ab initio calculations demonstrating the impact of the riboflavin wrapping pattern around the SWCNTs on their interaction with the allyl dextran gel.

Semiconductor nanochannels in metallic carbon nanotubes by thermomechanical chirality alteration.

Carbon nanotubes have a helical structure wherein the chirality determines whether they are metallic or semiconducting. Using in situ transmission electron microscopy, we applied heating and mechanical strain to alter the local chirality and thereby control the electronic properties of individual single-wall carbon nanotubes. A transition trend toward a larger chiral angle region was observed and explained in terms of orientation-dependent dislocation formation energy. A controlled metal-to-semiconductor transition was realized to create nanotube transistors with a semiconducting nanotube channel covalently bonded between a metallic nanotube source and drain. Additionally, quantum transport at room temperature was demonstrated for the fabricated nanotube transistors with a channel length as short as 2.8 nanometers.

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.