Search Results (2,660)

This study investigates the influence of vacancy engineering and nitrogen doping on the structural, electronic, and optical properties of T-graphene fragments (TFs) using density functional theory (DFT) and time-dependent DFT (TD-DFT). A central vacancy and five pyridinic nitrogen doping configurations are explored to modulate the optoelectronic behavior. All systems are thermodynamically stable, exhibiting tunable HOMO–LUMO gaps, orbital distributions, and charge transfer characteristics. Optical absorption spectra show redshifts and enhanced oscillator strengths in doped variants, notably v-NTF2 and v-NTF4. Nonlinear optical (NLO) analysis reveals significant enhancement in both static and frequency-dependent responses. v-NTF2 displays an exceptionally high first-order hyperpolarizability (⟨β⟩ = 1228.05 au), along with a strong electro-optic Pockels effect (β (−ω; ω, 0)) and second harmonic generation (β (−2ω; ω, ω)). Its third-order response, γ (−2ω; ω, ω, 0), also exceeds 1.2 × 10⁵ au under visible excitation. Conceptual DFT descriptors and energy decomposition analysis further supports the observed trends in reactivity, charge delocalization, and stability. These findings demonstrate that strategic nitrogen doping in vacancy-engineered TFs is a powerful route to tailor electronic excitation, optical absorption, and nonlinear susceptibility. The results offer valuable insight into the rational design of next-generation carbon-based materials for optoelectronic, photonic, and NLO device applications. Full article

Copper alloys are critical heat sink materials for fusion reactor divertors due to their high thermal conductivity (TC) and strength, yet their performance under extreme particle bombardment and heat fluxes in future tokamaks requires enhancement. While neutron-induced transmutation helium affects the properties of copper, the atomistic mechanisms linking helium bubble size to thermal transport remain unclear. This study employs non-equilibrium molecular dynamics (NEMD) simulations to isolate the effect of bubble diameter (10, 20, 30, 40 Å) on TC in copper, maintaining a constant He-to-vacancy ratio of 2.5. Results demonstrate that larger bubbles significantly impair TC. This reduction correlates with increased Kapitza thermal resistance and pronounced lattice distortion from outward helium diffusion, intensifying phonon scattering. Phonon density of states (PDOS) analysis reveals diminished low-frequency peaks and an elevated high-frequency peak for bubbles >30 Å, confirming phonon confinement and localized vibrational modes. The PDOS overlap factor decreases with bubble size, directly linking microstructural evolution to thermal resistance. These findings elucidate the size-dependent mechanisms of helium bubble impacts on thermal transport in copper divertor materials. Full article

Metal–organic frameworks (MOFs) have become a hot topic in various research fields nowadays. And MOF-derived metal oxides prepared by the sacrificial template method have been widely applied as catalysts for pollutant removal. Accordingly, we prepared a series of MOF-derived MnO_x catalysts with diverse morphologies (rod-like, flower-like, slab-like) via the pyrolysis of MOF precursors, and the as-prepared MnO_x catalysts demonstrated superior performance compared to the one prepared using the co-precipitation method. MnO_x-II, with a flower-like structure, exhibited excellent activity for formaldehyde (HCHO) catalytic ozonation at room temperature, reaching complete HCHO conversion at O₃/HCHO of 1.5 and more than 90% CO₂ selectivity at an O₃/HCHO ratio of 2.5. On the basis of various characterization methods, it was clarified that the enhanced catalytic performance of MnO_x-II benefited from its larger BET surface area, abundant oxygen vacancies, better redox ability at lower temperature, and more Lewis acid sites. The H₂O resistance and stability tests were also conducted. Furthermore, DFT calculations substantiated the enhanced adsorption of HCHO and O₃ on oxygen vacancies, while in–situ DRIFTS measurements elucidated the degradation pathway of HCHO during catalytic ozonation through detected intermediates. Full article

This article addresses the task of building personalized educational recommendations based on a heterogeneous knowledge graph that integrates data from university curricula, job vacancies, and online courses. To solve the problem of course recommendations by their relevance to a user’s competencies, a graph neural network (GNN)-based approach is proposed, specifically utilizing and comparing the Heterogeneous Graph Transformer (HGT) architecture, Graph Sample and Aggregate network (GraphSAGE), and Heterogeneous Graph Attention Network (HAN). Experiments were conducted on a heterogeneous graph comprising various node and relation types. The models were evaluated using regression and ranking metrics. The results demonstrated the superiority of the HGT-based recommendation model as a link regression task, especially in terms of ranking metrics, confirming its suitability for generating accurate and interpretable recommendations in educational systems. The proposed approach can be useful for developing adaptive learning recommendations aligned with users’ career goals. Full article

A concept towards current measurement in low and medium voltage power distribution networks is presented. The concentric magnetic field around the current-carrying conductor should be measured using a nitrogen-vacancy quantum magnetic field sensor. A bottleneck in current measurement systems is the readout electronics, which are usually based on optically detected magnetic resonance (ODMR). The idea is to have a hardware that tracks up to four resonances simultaneously for the detection of the three-axis magnetic field components and the temperature. Normally, expensive scientific instruments are used for the measurement setup. In this work, we present an electronic device that is based on a Zynq 7010 FPGA (Red Pitaya) with an add-on board, which has been developed to control the excitation laser, the generation of the microwaves, and interfacing the photodiode, and which provides additional fast digital outputs. The T1 measurement was chosen to demonstrate the ability to read out the spin of the system. Full article

The development of high-performance solid electrolytes is critical to advancing solid-state lithium-ion batteries (SSBs), with lithium lanthanum zirconium oxide (LLZO) emerging as a leading candidate due to its chemical stability and wide electrochemical window. In this study, we systematically investigated the effects of cation dopants, including aluminum (Al³⁺), tantalum (Ta⁵⁺), gallium (Ga³⁺), and rubidium (Rb⁺), on the structural, electronic, and ionic transport properties of LLZO using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. It appeared that, among all simulated results, Al-LLZO exhibits the highest ionic conductivity of 1.439 × 10⁻² S/cm with reduced activation energy of 0.138 eV, driven by enhanced lithium vacancy concentrations and preserved cubic-phase stability. Ta-LLZO follows, with a conductivity of 7.12 × 10⁻³ S/cm, while Ga-LLZO and Rb-LLZO provide moderate conductivity of 3.73 × 10⁻³ S/cm and 3.32 × 10⁻³ S/cm, respectively. Charge density analysis reveals that Al and Ta dopants facilitate smoother lithium-ion migration by minimizing electrostatic barriers. Furthermore, Al-LLZO demonstrates low electronic conductivity (1.72 × 10⁻⁸ S/cm) and favorable binding energy, mitigating dendrite formation risks. Comparative evaluations of radial distribution functions (RDFs) and XRD patterns confirm the structural integrity of doped systems. Overall, Al emerges as the most effective and economically viable dopant, optimizing LLZO for scalable, durable, and high-conductivity solid-state batteries. Full article

Although concentrated solar power (CSP) coupled with calcium looping (CaL) offers a promising avenue for efficient thermal chemical energy storage, calcium-based sorbents suffer from accelerated structural degradation and decreased CO₂ capture capacity during multiple cycles. This study used Density Functional Theory (DFT) calculations to investigate the mechanism by which Mg and Ni doping improves the adsorption/desorption performance of CaO. The DFT results indicate that Mg and Ni doping can effectively reduce the formation energy of oxygen vacancies on the CaO surface. Mg–Ni co-doping exhibits a significant synergistic effect, with the formation energy of oxygen vacancies reduced to 5.072 eV. Meanwhile, the O²⁻ diffusion energy barrier in the co-doped system was reduced to 2.692 eV, significantly improving the ion transport efficiency. In terms of CO₂ adsorption, Mg and Ni co-doping enhances the interaction between surface O atoms and CO₂, increasing the adsorption energy to −1.703 eV and forming a more stable CO₃²⁻ structure. For the desorption process, Mg and Ni co-doping restructured the CaCO₃ surface structure, reducing the CO₂ desorption energy barrier to 3.922 eV and significantly promoting carbonate decomposition. This work reveals, at the molecular level, how Mg and Ni doping optimizes adsorption–desorption in calcium-based materials, providing theoretical guidance for designing high-performance sorbents. Full article

One of the advantages of the EPR spectroscopy method in assessing structural defects caused by irradiation is the fact that using this method it is possible to determine not only the concentration dependences of the defect structure but to also establish their type, which is not possible with methods such as X-ray diffraction or scanning electron microscopy. Based on the data obtained, the role of variation in the ratio of components in Li₄SiO₄–Li₂TiO₃ ceramics on the processes of softening under high-dose irradiation with protons simulating the accumulation of hydrogen in the damaged layer, as well as the concentration of structural defects in the form of oxygen vacancies and radiolysis products on the processes of high-temperature degradation of ceramics, was determined. It was found that the main changes in the defect structure during the prolonged thermal exposure of irradiated samples are associated with the accumulation of oxygen vacancies, the density of which was estimated by the change in the intensity of singlet lithium, characterizing the presence of E-centers. At the same time, it was found that the formation of interphase boundaries in the structure of Li₄SiO₄–Li₂TiO₃ ceramics leads to the inhibition of high-temperature degradation processes in the case of post-radiation thermal exposure for a long time. Also, during the conducted studies, the role of thermal effects on the structural damage accumulation rate in Li₄SiO₄–Li₂TiO₃ ceramics was determined in the case when irradiation is carried out at different temperatures. During the experiments, it was determined that the main contribution of thermal action in the process of proton irradiation at a fluence of 5 × 10¹⁷ proton/cm² is an increase in the concentration of radiolysis products, described by changes in the intensities of spectral maxima, characterized by the presence of defects such as ≡Si–O, SiO₄³⁻ and Ti³⁺ defects. Full article

This study presents the development of Cu-doped NiMo/TiO₂ photoelectrocatalysts for simultaneous green hydrogen production and pharmaceutical pollutant removal under simulated solar irradiation. The catalysts were synthesized via wet impregnation (15 wt.% total metal loading with 0.6 wt.% Cu) and thermally treated at 400 °C and 900 °C to investigate structural transformations and catalytic performance. Comprehensive characterization (XRD, BET, SEM, XPS) revealed phase transitions, enhanced crystallinity, and redistribution of redox states upon Cu incorporation, particularly the formation of NiTiO₃ and an increase in oxygen vacancies. Crystallite sizes for anatase, rutile, and brookite ranged from 21 to 47 nm at NiMoCu400, while NiMoCu900 exhibited only the rutile phase with 55 nm crystallites. BET analysis showed a surface area of 44.4 m²·g⁻¹ for NiMoCu400, and electrochemical measurements confirmed its higher electrochemically active surface area (ECSA, 2.4 cm²), indicating enhanced surface accessibility. In contrast, NiMoCu900 exhibited a much lower BET surface area (1.4 m²·g⁻¹) and ECSA (1.4 cm²), consistent with its inferior photoelectrocatalytic performance. Compared to previously reported binary NiMo/TiO₂ systems, the ternary NiMoCu/TiO₂ catalysts demonstrated significantly improved hydrogen production activity and more efficient photoelectrochemical degradation of paracetamol. Specifically, NiMoCu400 showed an anodic peak current of 0.24 mA·cm⁻² for paracetamol oxidation, representing a 60% increase over NiMo400 and a cathodic current of −0.46 mA·cm⁻² at −0.1 V vs. RHE under illumination, nearly six times higher than the undoped counterpart (–0.08 mA·cm⁻²). Mott–Schottky analysis further revealed that NiMoCu400 retained n-type behavior, while NiMoCu900 exhibited an unusual inversion to p-type, likely due to Cu migration and rutile-phase-induced realignment of donor states. Despite its higher photosensitivity, NiMoCu900 showed negligible photocurrent, confirming that structural preservation and surface redox activity are critical for photoelectrochemical performance. This work provides mechanistic insight into Cu-mediated photoelectrocatalysis and identifies NiMoCu/TiO₂ as a promising bifunctional platform for integrated solar-driven water treatment and sustainable hydrogen production. Full article

Accelerated industrialization and surging energy demands have led to continuously rising atmospheric CO₂ concentrations. Developing sustainable methods to reduce atmospheric CO₂ levels is crucial for achieving carbon neutrality. Concurrently, the rapid development of new energy vehicles has driven a significant increase in demand for lithium-ion batteries (LIBs), which are now approaching an end-of-life peak. Efficient recycling of valuable metals from spent LIBs represents a critical challenge. This study employs conventional hydrometallurgical processing to recover valuable metals from spent LIBs. Subsequently, Ni-doped Co₃O₄ (Ni:Co₃O₄) supported on the natural mineral attapulgite (ATP) was synthesized via a sol–gel method. The incorporation of a small amount of Ni into the Co₃O₄ lattice generates oxygen vacancies, inducing a localized surface plasmon resonance (LSPR) effect, which significantly enhances charge carrier transport and separation efficiency. During the photocatalytic reduction of CO₂, the primary product CO generated by the Ni:Co₃O₄/ATP composite achieved a high production rate of 30.1 μmol·g⁻¹·h⁻¹. Furthermore, the composite maintains robust catalytic activity even after five consecutive reaction cycles. Full article

Carbon monoxide (CO) is a major toxic gas emitted from vehicle exhaust, industrial processes, and incomplete fuel combustion, posing serious environmental and health risks. Catalytic oxidation of CO into less harmful CO₂ is an effective strategy to reduce these emissions. In this study, we investigated the catalytic performance of platinum (Pt) single atoms doped on C₃N monolayers with various vacancy defects, including single carbon (C_V) and nitrogen (N_V) vacancies, using density functional theory (DFT) calculations. Our results demonstrate that Pt@N_V-C₃N exhibited the most favorable catalytic properties, with the highest O₂ adsorption energy (−3.07 eV). This performance significantly outperforms Pt atoms doped at other vacancies. It can be attributed to the strong binding between Pt and nitrogen vacancies, which contributes to its excellent resistance to Pt aggregation. CO oxidation on Pt@N_V-C₃N proceeds via the Eley–Rideal (ER2) mechanism with a low activation barrier of 0.41 eV for the rate-determining step, indicating high catalytic efficiency at low temperatures. These findings suggest that Pt@N_V-C₃N is a promising candidate for CO oxidation, contributing to developing cost-effective and environmentally sustainable catalysts. The strong binding of Pt atoms to the nitrogen vacancies prevents aggregation, ensuring the stability and durability of the catalyst. The kinetic modeling further revealed that the ER2 mechanism offers the highest reaction rate constants over a wide temperature range (273–700 K). The low activation energy barrier also facilitates CO oxidation at lower temperatures, addressing critical challenges in automotive and industrial pollution control. This study provides valuable theoretical insights for designing advanced single-atom catalysts for environmental remediation applications. Full article

Graphene, a remarkable two-dimensional material, enhances the mechanical properties of high-entropy alloys as a reinforcing phase. This study investigated the influence of vacancy defects in graphene on the strengthening effect of FeNiCrCoCu high-entropy alloy through molecular dynamics simulations. The findings reveal that vacancy defects diminish graphene’s strength, resulting in its premature failure. In tensile tests, graphene with defects lowers the yield stress of the composite, yet it retains the ability to impede dislocations. Conversely, graphene exhibits a more pronounced strengthening effect during compression. Specifically, when the deletion of C atoms is less than 1%, the impact is negligible; between 1% and 6%, the strengthening effect diminishes; and when it surpasses 6%, the strengthening effect virtually ceases to exist. This research offers a theoretical foundation for optimizing graphene-reinforced composites. Full article

Accurate evaluation of the thermal conductivity of UO₂ with defects is very significant for optimizing fuel performance and enhancing the safety design of reactors. We employed a method that combines the Boltzmann transport equation with DFT+U to calculate the thermal conductivity of UO₂ containing fission products and irradiation-induced point defects. Our investigation reveals that the thermal conductivity of UO₂ is influenced by defect concentration, defect type, and temperature. Fission products and irradiation defects result in a decrease in thermal conductivity, but they have markedly different impacts on phonon scattering mechanisms. Metal cations tend to scatter low-frequency phonons (less than 5.8 THz), while the fission gas xenon scatters both low-frequency and high-frequency phonons (greater than 5.8 THz), depending on its occupancy at lattice sites. Uranium vacancies scatter low-frequency phonons, while oxygen vacancies scatter high-frequency phonons. When uranium and oxygen vacancies coexist, they scatter phonons across the entire frequency spectrum, which further results in a significant reduction in the thermal conductivity of UO₂. Our calculated results align well with experimental data across a wide temperature range and provide fundamental insights into the heat transfer mechanisms in irradiated UO₂. These findings are essential for establishing a thermal conductivity database for UO₂ under various irradiation conditions and benefit the development of advanced high-performance UO₂ fuel. Full article

The widespread adoption of sodium-ion batteries (SIBs) remains constrained by the inherent limitations of conventional anode materials, particularly their inadequate electronic conductivity, limited active sites, and pronounced structural degradation during cycling. To overcome these limitations, we propose a novel redox engineering approach to fabricate oxygen-vacancy-rich SnO₂ dots anchored on reduced graphene oxide (rGO), which are encapsulated within N-doped carbon nanofibers (denoted as ov-SnO₂/rGO@N-CNFs) through electrospinning and subsequent carbonization. The introduction of rich oxygen vacancies establishes additional sodium intercalation sites and enhances Na⁺ diffusion kinetics, while the conductive N-doped carbon network effectively facilitates charge transport and mitigates SnO₂ aggregation. Benefiting from the well-designed architecture, the hierarchical ov-SnO₂/rGO@N-CNFs electrode achieves remarkable reversible specific capacities of 351 mAh g⁻¹ after 100 cycles at 0.1 A g⁻¹ and 257.3 mAh g⁻¹ after 2000 cycles at 1.0 A g⁻¹ and maintains 177 mAh g⁻¹ even after 8000 cycles at 5.0 A g⁻¹, demonstrating exceptional long-term cycling stability and rate capability. This work offers a versatile design strategy for developing high-performance anode materials through synergistic interface engineering for SIBs. Full article

Nitrogen vacancy (NV) diamonds are promising room temperature quantum sensors. As the technology moves towards application, efficient use of energy and cost become critical for miniaturization. This work focuses on microwave-based spin control using the short-circuited end of a slot line, analyzed by finite element method (FEM) for magnetic field amplitude and uniformity. A microstrip-to-slot-line converter with a $-10$ dB bandwidth of $3.2$ GHz was implemented. Rabi oscillation measurements with an NV microdiamond on a glass fiber show uniform excitation over $1.5$ MHz across the slot, allowing spin manipulation within the coherence time of the NV center. Full article