Sergey N. Rashkeev

Heavy metal contamination in coastal and ballast waters motivates the development of low-cost, environmentally compatible filtration media. This study investigates how 6 MeV electron-beam irradiation (0–100 Gy) modifies the surface electronic and chemical properties of quartz-rich Baltic Sea sands collected from four Latvian coastal locations (Riga, Salacgriva, Ventspils, and Liepaja), and how these modifications affect chromium removal from aqueous K₂CrO₄ solutions. Surface electronic behavior was evaluated by near-threshold photoelectron emission spectroscopy (PEES), including electron work function (EWF) and analysis of differentiated spectra, while irradiation-associated changes in near-surface chemistry were assessed by X-ray photoelectron spectroscopy (XPS). Filtration performance was quantified by UV–Vis absorbance of filtrates. Across all sands, EWF values remained within ~4.7–4.9 eV; however, irradiation effects were strongly site-dependent. Liepaja sand exhibited the most pronounced response, including an EWF increase at 40 Gy, a shift in the differentiated PEES peak toward higher photon energies at ≥40 Gy, and the largest integrated photoemission intensity across doses, consistent with an elevated relative photoemission response under identical acquisition and processing conditions. XPS trends for Liepaja were consistent with irradiation-driven modification of the Si–O environment, while other sites showed comparatively minor changes. Filtration results mirrored these observations: Liepaja sand demonstrated the clearest dose-dependent enhancement in chromium removal with a non-monotonic feature at 40 Gy, consistent with competing formation and transformation of oxygen-related surface-reactive centers. Overall, the results show that electron-beam irradiation can modestly enhance Cr(VI) removal by natural quartz sands, with the magnitude governed by site-specific near-surface electronic structure and its dose-dependent evolution.

Interfaces formed by high energy density materials and metal oxides present intriguing new opportunities for a large set of novel applications that depend on the control of the energy release and initiation of explosive chemical reactions. We studied the role of structural defects at a MgO surface in the modification of electronic and optical properties of the energetic material TNT (2-methyl-1,3,5-trinitrobenzene, also known as trinitrotoluene, C₇H₅N₃O₆) deposited at the surface. Using density functional theory (DFT)-based solid-state periodic calculations with hybrid density functionals, we show how the control of chemical explosive reactions can be achieved by tuning the electronic structure of energetic compound at an interface with oxides. The presence of defects at the oxide surface, such as steps, kinks, corners, and oxygen vacancies, significantly affects interfacial properties and modifies electronic spectra and charge transfer dynamics between the oxide surface and adsorbed energetic material. As a result, the electronic and optical properties of trinitrotoluene, mixed with an inorganic material (thus forming a composite), can be manipulated with high precision by interactions between TNT and the inorganic material at composite interfaces, namely, by charge transfer and band alignment. Also, the electron charge transfer between TNT and MgO surface reduces the decomposition barriers of the energetic material. In particular, it is shown that surface structural defects are critically important in the photodecomposition processes. These results open new possibilities for the rather precise control over the decomposition initiation mechanisms in energetic materials by optical excitations.

Transition-metal oxides with pyroxene structure, such as alkali-metal metavanadates, are known for their good chemical stability and have been used accordingly in many applications. In this work, we explore the possibility of enhancing the carrier transport and optoelectronic properties of hybrid inorganic–organic metavanadates MVO₃ by introducing molecular cations. The hydrogen bonded molecular cations are found to enhance the electronic effective dimensionality of the system. This is related to the connectivity of the atomic orbitals to form new electron and hole transport channels. For the materials considered here, these channels are formed by hydrogen bonding that, besides enhancing the stability, results in enhanced macroscopic electronic transport and enhanced photo-generated carriers relaxation time. Our study indicates that the electronic dimensionality of the hybrid metavanadates could exceed their subnanometer structural dimensionality which is a desirable feature for improving their optoelectronic properties. This concept can be generalized to a wider class of hybrid organic–inorganic frameworks.

Improving the stability of hybrid perovskite solar cells is believed to be the main step toward large scale commercialization of this technology. In this work, we demonstrate that the stability can be enhanced significantly by proper fluorination of the methylammonium cation. A systematic study to identify the optimal stability of the perovskite material with low controlled concentrations of modified cations was conducted using density functional theory (DFT). Our results suggest a route to enhance the thermodynamic stability of hybrid inorganic–organic perovskites, while at the same time reduce the ionic diffusion. The optimal fluorination has no significant impact on the band gap or the volume expansion of the CH₃NH₃PbI₃ perovskite. We demonstrate that the fluorination has a tendency to stabilize the material due to the strengthening of some initially weak hydrogen bonds between MA⁺ cations and the surrounding lead-iodide framework. The observed strengthening is the result of internal structural deformations which are related to the formation of long C–N bonds. Finally, we showed through calculation that fluorination should reduce significantly the iodine vacancy mediated diffusion in the perovskite under applied bias voltage.

We investigated the possibility of band structure engineering of pyroxene silicates with chemical formula A⁺¹B⁺³Si₂O₆ by proper cation substitution. Typically, band gaps of naturally formed pyroxene silicates such as NaAlSi₂O₆ are quite high (≈5 eV). Therefore, it is important to find a way to reduce band gaps for these materials below 3 eV to make them usable for optoelectronic applications operating at visible light range of the spectrum. Using first‐principles calculations, we found that appropriate substitutions of both A⁺ and B³⁺ cations can reduce the band gaps of these materials to as low as 1.31 eV. We also discuss how the band gap in this class of materials is affected by cation radii, electronegativity of constituent elements, spin‐orbit coupling, and structural modifications. In particular, the replacement of Al³⁺ in NaAlSi₂O₆ by another trivalent cation Tl³⁺ results in the largest band‐gap reduction and emergence of intermediate bands. We also found that all considered materials are still thermodynamically stable. This work provides a design approach for new environmentally benign and abundant materials for use in photovoltaics and optoelectronic devices.