Search Results (120)

Halide double perovskites with near-infrared (NIR) emission are promising for optoelectronic applications. NIR-II (1000–1700 nm) emission, in particular, is attractive due to its strong tissue penetration, high spatial resolution, and low biological light damage risk. However, materials capable of NIR-II emission often require additional sensitizers and suffer from issues such as narrow emission bandwidth and low photoluminescence efficiency. In this work, we report a Re⁴⁺ doping strategy using Cs₂WCl₆, a vacancy–ordered double perovskite, to achieve efficient NIR-II emission. Spectroscopic and dynamic measurements reveal energy transfer between the Cs₂WCl₆ matrix and the Re⁴⁺ centers, resulting in efficient broadband NIR-II emission centered at 1345 nm (FWHM ≈ 87 nm), along with broad excitation ranging from 250 to 850 nm. The optimal NIR-II emission occurs at 1345 nm with a photoluminescence quantum yield (PLQY) of 29.83% when the Re⁴⁺ doping concentration is 1%. This work demonstrates an efficient, sensitizer-free method for achieving broadband NIR-II emission and provides a new material strategy for high–performance double perovskites NIR light sources. Full article

The field of developing effective catalysts for heterogeneous catalysis has recently focused on controlling the structures of catalysts themselves to optimise the density and energy of crystal lattice defects. This can significantly influence catalytic activity in terms of both reaction rates and reaction mechanisms, and thus the selective production of desired substances as well. In many cases, these crystal lattice defects manifest themselves as so-called electron traps (ETs) and thus significantly influence charge transfer between the catalyst and reactants. ETs provide the missing electronic link between atomic-scale defects and macroscopic performance in heterogeneous catalysis. Therefore, the importance of ETs for catalysis is particularly evident in areas where charge transfer plays a fundamental role in the reaction mechanism, such as photocatalysis and electrocatalysis. In the field of thermally initiated reactions, the importance of ETs in heterogeneous catalysis has not yet been fully appreciated. However, several studies have already addressed the importance of ETs for this type of reaction. This review consolidates and extends the concept of ETs to purely thermal-initiated reactions, with a focus on CO₂ hydrogenation using typical transition metal catalysts. Firstly, in this review, ETs are defined as band gap states associated with internal and external defects, and their depth, density, spatial location, and dynamics are then coupled with key steps in thermocatalytic cycles, including charge storage/release, reactant activation, intermediate stabilisation, and redox turnover. Secondly, electron trap detection is reviewed based on advanced spectroscopic techniques, including reversed double-beam photoacoustic spectroscopy (RDB-PAS), thermally stimulated current (TSC), deep-level transient spectroscopy (DLTS), thermoluminescence (TL), electron paramagnetic resonance (EPR), and photoluminescence (PL), highlighting how each method describes trap energetics and populations under realistic operating conditions. Finally, case studies on the application of metal oxides and supported metals are discussed, as these are typical catalysts for the reaction mentioned above. This review highlights how oxygen vacancies (OVs), polarons, and metal–support interfacial sites act as robust electron reservoirs, lowering the barriers for CO₂ activation and hydrogenation. By reframing thermocatalysts through the lens of ET chemistry, this review identifies ETs as actionable targets for the rational design of next-generation materials for CO₂ hydrogenation and related high-temperature transformations. Full article

Electrochemical water splitting for hydrogen production is limited by the slow kinetics of the oxygen evolution reaction (OER). The tunable structure and anion-exchange capability of layered double hydroxides (LDHs) underpin their promise as OER catalysts. Consequently, the strategic incorporation of foreign anions is viewed as a powerful approach to engineer their active sites and boost catalytic activity. This review summarizes how doping with anions such as NO₃⁻, PO₄³⁻, Cl⁻, F⁻, and Sq²⁻ modifies the electronic structure of LDHs. These anions regulate the local coordination environment, induce oxygen vacancies, and alter metal oxidation states, thereby synergistically optimizing both the adsorption–evolution mechanism (AEM) and the lattice oxygen oxidation mechanism (LOM). For instance, NO₃⁻ promotes surface reconstruction, F⁻ activates lattice oxygen, PO₄³⁻ stabilizes the interface, Cl⁻ reshapes reaction pathways, and Sq²⁻ maintains interfacial alkalinity. Collectively, rational anion engineering lowers the overpotential, increases current density, and improves stability, establishing an effective design framework for advanced LDH-based OER electrocatalysts. Full article

Defective graphene has emerged as a promising strategy to enhance electrochemical performance of pristine graphene (p-Gr) as anodes in lithium-ion batteries (LIBs). Herein, we perform a comprehensive first-principles study based on density functional theory (DFT) to systematically investigate the Li adsorption, charge transfer, and diffusion behaviors of p-Gr and defective graphene (d-Gr) with single vacancy (SV Gr) and double vacancy (DV5-8-5 Gr) defects, aiming to clarify the mechanism by which defects modulate Li storage performance. Structural optimization reveals that SV Gr undergoes notable out-of-plane distortion after Li adsorption, while DV5-8-5 Gr retains planar geometry but exhibits more significant C-C bond length variations compared to p-Gr. Binding energy results confirm that defects enhance Li adsorption stability, with DV5-8-5 Gr showing the strongest Li–graphene interaction, followed by SV Gr and p-Gr. Bader charge analysis and charge density difference plots further validate that defects enhance charge transfer from Li ions to graphene. Using the nudged elastic band (NEB) method, we find that defects reduce Li diffusion barriers: DV5-8-5 Gr exhibits a lower barrier than p-Gr. Our findings demonstrate that DV5-8-5 Gr exhibits the most favorable Li storage performance, providing a robust theoretical basis for designing high-performance graphene anodes for next-generation LIBs. Full article

Auger decay of all levels of the double core-hole states $4d^{-2}$ of Xe²⁺, including collective Auger decay (CAD) pathways, is investigated using the relativistic distorted-wave approximation. Large-scale configuration interaction calculations were performed to obtain level-to-level Auger decay rates. In addition to the typical Auger decay final levels associated with the configurations of $4d^{-1}5s^{2}5p^4$, $4d^{-1}5s^{1}5p^5$, and $4d^{-1}5s^{0}5p^6$, evident contributions are identified from excited channels, leading to configurations such as $4d^{9}4f^{1}5s^{2}5p^3$, $4d^{9}5s^{2}5p^{3}5d^1$, $4d^{9}5s^{2}5p^{3}6s^1$, and $4d^{9}5s^{2}5p^{3}6p^1$. These contributions arise from strong electron correlation between the valence electronic orbitals and the $4d$ inner-shell orbital. The CAD rates and branching ratios (BRs) are determined for each double core-hole level with a minimum CAD BR of 1.28% and a maximum of 4.08% among all CAD channels. The configuration-averaged CAD BR is predicted to be 1.93%, which helps explain recent unexplained experimental findings. The inclusion of CAD processes enriches Auger electron spectroscopy, thereby extending potential applications of this important experimental tool in both fundamental and applied research. Full article

A novel strategy was adopted to enhance the energy storage properties of materials through constructing a vacancy defect. BaTi_1−xCu_xO_3−x (abbreviated as BTCx, x = 0–0.05) ceramics were prepared. The influences of Cu doping on structure and electrical properties were systematically investigated in this study. The result reveals that the oxygen vacancies in BTCx ceramics can inhibit grain growth and improve breakdown strength. Notably, as Cu content increases, the abundance of oxygen vacancies of the BTCx ceramics intensifies the relaxor behavior and induces double hysteresis loops with high energy storage performance. The excellent energy storage density of 1.34 J/cm³ and efficiency of 90.1% were achieved for BTC3 ceramics at 180 kV/cm, which indicates that the outstanding energy storage properties of BTCx ceramics make them have broad application prospects in advanced pulse power capacitors. Full article

Solid-state spin centers are at the forefront of developing advanced quantum technologies, engaging in applications of sensing, communication and computing. A semiconductor host matrix compatible with existing silicon technology provides a robust platform for holding spin defects and an opportunity for external manipulation. In this article, negatively charged nitrogen-vacancy (NV) centers in the hexagonal hh position in a 6H polytype silicon carbide crystal was studied using high-frequency (94 GHz) electron paramagnetic (EPR) and electron nuclear double resonances (ENDOR) spectroscopy. Experimentally determined values of hyperfine and quadrupole interactions of ¹⁴N were compared with the values obtained for the centers in NV_k2k1 positions. The distribution of spin density of the defect within a supercell of the SiC crystal lattice was calculated using the density functional theory approach. The theoretical estimation of electron-nuclear interaction constants turned out to be in close agreement with the experimental values, which allows us to refine the microscopic model of a point defect. The temperature dependence of the spin Hamiltonian values (δA/δT ≅ 180 Hz/K) was studied with the possibility of observing the ¹⁴N NMR signal at room temperature. The fundamental knowledge gained about interactions’ parameters’ behavior lays the foundation for the creation of promising quantum platforms. Full article

The activation and dissociation of O₂ molecules play a key role in the oxidation of toxic gas molecules and the oxygen reduction reaction (ORR) in hydrogen–oxygen fuel cells. The interactions between O₂ molecules and the surfaces of Fe-doped γ-graphyne were systematically explored, mainly adopting the combined method of the density functional theory with dispersion correction (DFT-D3) and the climbing image nudged elastic band (CI-NEB) method. The order of the formation energy values of these defective systems is E_f(Fe_C2) < E_f(Fe_C1) < E_f(Fe_D1) < E_f(V_C1) < E_f(V_D1) < E_f(V_C2) < E_f(Fe_D2) < E_f(V_D2), which indicates that the process of Fe dopant atoms substituting single-carbon atoms/double-carbon atoms is relatively easier than the formation of vacancy-like defects. The results of ab initio molecular dynamics (AIMD) simulations confirm that the doped systems can maintain structural stability at room temperature conditions. Fe-doped atoms transfer a certain amount of electrons to the adsorbed O₂ molecules, thereby causing an increase in the O-O bond length of the adsorbed O₂ molecules. The electrons obtained by the anti-bonding 2π* orbitals of the adsorbed O₂ molecules are mainly derived from the 3d orbitals of Fe atoms. There is a competitive relationship between the substrate’s carbon atoms and the adsorbed O₂ molecules for the charges transferred from Fe atoms. In the C1 and C2 systems, O₂ molecules have a greater advantage in electron accepting ability compared to the substrate’s carbon atoms. The elongation of O-O bonds and the amount of charge transfer exhibit a positive relationship. More electrons are transferred from Fe-3d orbitals to adsorbed O₂ molecules, occupying the 2π* orbitals of adsorbed O₂ molecules, further elongating the O-O chemical bond until it breaks. The dissociation process of adsorbed O₂ molecules on the surfaces of GY-Fe systems (C2 and D2 sites) involves very low energy barriers (0.016 eV for C2 and 0.12 eV for D2). Thus, our studies may provide useful insights for designing catalyst materials for oxidation reactions and the oxygen reduction reaction. Full article

The magnetic resonance frequency-locking technique is recognized as an effective approach for simultaneously improving the dynamic range, performance stability, and measurement precision of diamond nitrogen vacancy (NV)-center magnetometers. Nevertheless, insufficient research on sensitivity limits the overall performance of frequency-locking diamond magnetometers. In this paper, we propose a dual-magnetic-resonance-frequency-locking (MRFL) differential detection method. Theoretical and experimental results demonstrate that the scaling factor between the sensor output and the magnetic field is doubled compared with that under the single-MRFL method, and the proposed method also enables alternating current (AC) magnetic field detection. The proposed system exhibits a measurement range from −0.29 mT to 0.30 mT. Furthermore, a sensitivity of 0.56 nT/√Hz is achieved, representing a 58.2% improvement relative to that of the single-MRFL method. Our work provides a viable solution for accelerating the transition of frequency-locking diamond magnetometers from laboratory research to practical applications. Full article

The need for energy storage and the rapid development of new electronic platforms have prompted intense research into small and secure energy storage devices, particularly supercapacitors (SCs). Layered double hydroxides (LDHs) are potential electrode materials for SCs because of their excellent physicochemical and electrical characteristics. They involve interlayer spacing, high oxidation states, simplicity of synthesis, and distinct morphologies. Despite their potential, several kinds of LDHs still face constraints, such as particle aggregation, moderate surface area, and high resistance, which limit their use in energy storage. To overcome these challenges and enhance the electrochemical performance of LDHs, they have used strategies such as anion intercalation, oxygen vacancy, heteroatom, surfactant, fluorine, and metal doping, which have been demonstrated as electrode materials for SCs. Therefore, this review discusses recent advances in different LDHs and studies comparing bare and modified LDH for three- and two-electrode systems, with an emphasis on their morphologies, surface areas, and electrical properties for SC applications. It was found that modified LDHs achieve enhanced electrochemical performance in comparison to their corresponding bare LDHs. Consequently, there are potential opportunities to modify the surface of the recently invented LDHs for electrochemical investigations, which could result in improving their performance. This review also presents future perspectives on LDH-based energy storage devices for supercapacitors. Full article

The rising demand for clean energy, especially hydrogen, has heightened the need for efficient storage materials. Perovskites, with their unique structures, show great promise for hydrogen storage and optical uses. To identify promising candidates for hydrogen storage materials, the mechanical, electronic, and optical properties of four ordered vacancy double perovskite structures X₂MH₆ (Ba₂BeH₆, Ba₂MgH₆, Ca₂BeH₆, and Sr₂MgH₆) were predicted using density functional theory. These materials were confirmed to be stable, and their hydrogen storage capacity, mechanical properties, electronic structures, and optical performance were thoroughly analyzed. Ca₂BeH₆ demonstrated the highest gravimetric (6.32%) and volumetric (32.29 g·H₂/L) hydrogen storage capacity, showcasing its exceptional potential. It should be noted that the hydrogen storage capacities reported here are theoretical estimates based solely on structural models, and this study does not assess the practical storage and delivery performance of these materials. Its mechanical stiffness and near-isotropic properties further enhance its practicality. Electrical studies revealed all four materials are semiconductors, all of them are direct semiconductors. Optical properties were analyzed via dielectric functions, offering key insights for designing advanced hydrogen storage and optical materials. Full article

The effect of strontium substitution on the crystal tructure, as well as the magnetic, and electrical properties of lanthanum ferrite (LaFeO₃) synthesized by high-energy ball milling, is studied, with an emphasis on magnetodielectric coupling. X-ray diffraction (XRD) confirmed the successful synthesis of orthorhombic La_1−xSr_xFeO₃ for doping levels up to 0.2 mol. At 0.3 mol Sr²⁺, two phases appear: La_0.6Sr_0.4FeO_2.976 and La_0.8Sr_1.2FeO_3.714, the latter being metastable. This phase vanishes at 0.5 mol. The Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis confirmed these results using a vibrating sample magnetometer (VSM), whose measurements show ferromagnetism at 0.1 and 0.3 mol Sr²⁺, attributed to crystal distortion, magnetic spin rearrangement, and as consequence, modifications in the double-exchange interactions. Dielectric tests reveal that higher Sr²⁺ concentrations lead to increased relative permittivity, dielectric losses, and conductivity, linked to oxygen vacancy formation. This study demonstrates a room-temperature magnetodielectric coupling of 32% in Sr-doped lanthanum ferrite, highlighting its potential for technological applications. Full article

The oxygen evolution reaction (OER) is pivotal in hydrogen production via water electrolysis, yet its sluggish kinetics, stemming from the four-electron transfer process, remain a major obstacle, with overpotential reduction being critical for enhancing efficiency. This work addresses this challenge by developing a novel approach to stabilize and activate non-precious metal catalysts for OER. Specifically, we synthesized a three-dimensional flake NiFe-LDH/ZIF-L composite catalyst on a flexible nickel foam (NF) substrate through a room temperature soaking and hydrothermal method, leveraging the mesoporous structure of ZIF-L to increase the specific surface area and optimizing electron transfer pathways via interfacial regulation. Continuous linear sweep voltammetry (LSV) scanning induced structural self-reconstruction, forming highly active NiOOH species enriched with oxygen vacancies, which significantly boosted catalytic performance. Experimental results demonstrate an overpotential of only 221 mV at 10 mA cm⁻² and a Tafel slope of 56.3 mV dec⁻¹, alongside remarkable stability, attributed to the catalyst’s hierarchical nanostructure that accelerates mass diffusion and charge transfer. The innovation lies in the synergistic effect of the mesoporous ZIF-L structure and interfacial regulation, which collectively enhance the catalyst’s activity and durability, offering a promising strategy for advancing large-scale water electrolysis hydrogen production technology. Full article

In order to solve the self-heating problem of power electronic devices, this paper adopts a nonequilibrium molecular dynamics approach to study the thermal transport regulation mechanism of the aluminum nitride/graphene/silicon carbide heterogeneous interface. The effects of temperature, size, and vacancy defects on interfacial thermal conductivity are analyzed by phonon state density versus phonon participation rate to reveal their phonon transfer mechanisms during thermal transport. It is shown that the interfacial thermal conductance (ITC) increases about three times when the temperature increases from 300 K to 1100 K. It is analyzed that the increase in temperature will enhance lattice vibration, enhance phonon coupling degree, and thus increase its ITC. With the increase in the number of AlN-SiC layers from 8 to 28, the ITC increases by about 295.3%, and it is analyzed that the increase in the number of AlN-SiC layers effectively reduces the interfacial scattering and improves the phonon interfacial transmission efficiency. The increase in the number of graphene layers from 1 layer to 4 layers decreases the ITC by 70.3%. The interfacial thermal conductivity reaches a minimum, which is attributed to the increase in graphene layers aggravating the degree of phonon localization. Under the influence of the increase in graphene single and double vacancy defects concentration, the ITC is slightly reduced. When the defect rate reaches about 20%, the interfacial thermal conductance of SV (single vacancy) and DV (double vacancy) defects rises back to 5.606 × 10⁻² GW/m²K and 5.224 × 10⁻² GW/m²K, respectively. It is analyzed that the phonon overlapping and the participation rate act at the same time, so the heat-transferring phonons increase, increasing the thermal conductance of their interfaces. The findings provide theoretical support for optimizing the thermal management performance of heterostructure interfaces. Full article

The novel sub-stoichiometric copper oxide CuO_0.75 was prepared via the slow oxidation of Cu₂O. This compound retains the original crystallographic structure of tenorite CuO, despite the considerable presence of disordered oxygen vacancies. CuO_0.75 resembles the mixed valence oxide Cu²⁺/Cu¹⁺, while the unit cell contains one oxygen vacancy. Performance-wise, the electric resistivity and magnetic susceptibility data follow the Anderson–Mott localization theories. The exponential localization decay length was found to be α⁻¹ = 2.1 nm, in line with modern scaling research. Via cooling, magnetic double-exchange interaction, mediated by oxygen, results in Zener conductivity at T~122 K, which is followed by antiferromagnetic transition at T~51 K. The obtained results indicate that the CuO_0.75 compound can be perceived as a showcase material for the demonstration of a new class of high-performance magnetic materials. Full article