Search Results (553)

Despite significant progress in photoelectrochemical (PEC) water splitting, high fabrication costs and limited efficiency of photoanodes hinder practical applications. Bismuth vanadate (BiVO₄), with its low cost, non-toxicity, and suitable band structure, is a promising photoanode material but suffers from poor charge transport, sluggish surface kinetics, and photocorrosion. In this study, porous monoclinic BiVO₄ films are fabricated via a simplified successive ionic layer adsorption and reaction (SILAR) method, followed by borate treatment and PEC deposition of NiFeO_x. The resulting B/BiVO₄/NiFeO_x photoanode exhibits a significantly enhanced photocurrent density of 2.45 mA cm⁻² at 1.23 V vs. RHE—5.3 times higher than pristine BiVO₄. It also achieves an ABPE of 0.77% and a charge transfer efficiency of 79.5%. These results demonstrate that dual surface modification via borate and NiFeO_x is a cost-effective strategy to improve BiVO₄-based PEC water splitting performance. This work provides a promising pathway for the scalable development of efficient and economically viable photoanodes for solar hydrogen production. Full article

The electrochemical reduction of carbon monoxide (COER) offers a promising route for generating value-added multi-carbon (C₂₊) products, such as ethanol, but achieving high catalytic performance remains a significant challenge. Herein, we performed comprehensive density functional theory (DFT) computations to evaluate CO-to-ethanol conversion on single metal atoms anchored on graphitic carbon nitride (TM/g–CN). We showed that these metal atoms stably coordinate with edge N sites of g–CN to form active catalytic centers. Screening 20 TM/g–CN candidates, we identified V/g–CN and Zn/g–CN as optimal catalysts: both exhibit low free-energy barriers (<0.50 eV) for the key ^*CO hydrogenation steps and facilitate C–C coupling via an Eley–Rideal mechanism with a negligible kinetic barrier (~0.10 eV) to yield ethanol at low limiting potentials, which explains their superior COER performance. An analysis of d-band centers, charge transfer, and bonding–antibonding orbital distributions revealed the origin of their activity. This work provides theoretical insights and useful guidelines for designing high-performance single-atom COER catalysts. Full article

The one-dimensional (1D) Sb(III)-based organic–inorganic hybrid perovskite (AImd)₂¹_∞[SbI₅] (AImd = 1-allylimidazolium) crystallizes in the orthorhombic, centrosymmetric space group Pnma. The structure consists of corner-sharing [SbI₆] octahedra forming 1D chains separated by allylimidazolium cations. Void analysis through Mercury CSD software confirmed a densely packed lattice with a calculated void volume of 1.1%. Integrated quantum theory of atoms in molecules (QTAIM) and non-covalent interactions index (NCI) analyses showed that C–H···I interactions between the cations and the ¹_∞[SbI₅]²⁻ network predominantly stabilize the supramolecular assembly followed by N–H···I hydrogen bonds. The calculated growth morphology (GM) model fits very well to the experimental morphology. UV–Vis diffuse reflectance spectroscopy allowed us to determine the optical band gap to 3.15 eV. Density functional theory (DFT) calculations employing the B3LYP, CAM-B3LYP, and PBE0 functionals were benchmarked against experimental data. CAM-B3LYP best reproduced Sb–I bond lengths, while PBE0 more accurately captured the HOMO–LUMO gap and the associated electronic descriptors. These results support the assignment of an inorganic-to-organic [Sb–I] → π* charge-transfer excitation, and clarify how structural dimensionality and cation identity shape the material’s optoelectronic properties. Full article

This study employs density functional theory (DFT) to investigate the electronic and optical properties of molybdenum (Mo) and chalcogen (S, Se, Te) co-doped anatase TiO₂. Two co-doping configurations were examined: Model 1, where the dopants are adjacent, and Model 2, where the dopants are farther apart. The incorporation of Mo into anatase TiO₂ resulted in a significant bandgap reduction, lowering it from 3.22 eV (pure TiO₂) to range of 2.52–0.68 eV, depending on the specific doping model. The introduction of Mo-4d states below the conduction band led to a shift in the Fermi level from the top of the valence band to the bottom of the conduction band, confirming the n-type doping characteristics of Mo in TiO₂. Chalcogen doping introduced isolated electronic states from Te-5p, S-3p, and Se-4p located above the valence band maximum, further reducing the bandgap. Among the examined configurations, Mo–S co-doping in Model 1 exhibited most optimal structural stability structure with the fewer impurity states, enhancing photocatalytic efficiency by reducing charge recombination. With the exception of Mo–Te co-doping, all co-doped systems demonstrated strong oxidation power under visible light, making Mo-S and Mo-Se co-doped TiO₂ promising candidates for oxidation-driven photocatalysis. However, their limited reduction ability suggests they may be less suitable for water-splitting applications. The study also revealed that dopant positioning significantly influences charge transfer and optoelectronic properties. Model 1 favored localized electron density and weaker magnetization, while Model 2 exhibited delocalized charge density and stronger magnetization. These findings underscore the critical role of dopant arrangement in optimizing TiO₂-based photocatalysts for solar energy applications. Full article

Titanium dioxide (TiO₂) is a benchmark photocatalyst for environmental applications, but its limited visible-light activity due to a wide band gap and fast charge recombination restricts its practical efficiency. This study presents the development of heterostructured Ag (Au)/MoS₂-TiO₂ inverse opal (IO) films that synergistically integrate photonic, plasmonic, and semiconducting functionalities to overcome these limitations. The materials were synthesized via a one-step evaporation-induced co-assembly approach, embedding MoS₂ nanosheets and plasmonic nanoparticles (Ag or Au) within a nanocrystalline TiO₂ photonic framework. The inverse opal architecture enhances light harvesting through slow-photon effects, while MoS₂ and plasmonic nanoparticles improve visible-light absorption and charge separation. By tuning the template sphere size, the photonic band gap was aligned with the TiO₂-MoS₂ absorption edge and the localized surface plasmon resonance of Ag, enabling optimal spectral overlap. The corresponding Ag/MoS₂-TiO₂ photonic films exhibited superior photocatalytic and photoelectrocatalytic degradation of tetracycline under visible light. Ultraviolet photoelectron spectroscopy and Mott–Schottky analysis confirmed favorable band alignment and Fermi level shifts that facilitate interfacial charge transfer. These results highlight the potential of integrated photonic–plasmonic-semiconductor architectures for efficient solar-driven water treatment. Full article

Penta-graphene, a novel two-dimensional carbon allotrope entirely composed of pentagonal carbon rings, has attracted increasing attention due to its unique geometric structure, mechanical robustness, and intrinsic semiconducting nature. In this study, we systematically investigate the adsorption behavior of three typical dissolved gases in transformer oil (CO, C₂H₂, and C₂H₄) on penta-graphene using first-principles calculations based on density functional theory. The optimized adsorption configuration, adsorption energy, charge transfer, adsorption distance, band structure, density of states, charge density difference, and desorption time are analyzed to evaluate the sensing capability of penta-graphene. Results reveal that penta-graphene exhibits moderate chemical interactions with CO and C₂H₂, accompanied by noticeable charge transfer and band structure changes, whereas C₂H₄ shows weaker physisorption characteristics. The projected density of states analysis further confirms the orbital hybridization between gas molecules and the substrate. Additionally, the desorption time calculations suggest that penta-graphene possesses good sensing and recovery potential, especially under elevated temperatures. These findings indicate that penta-graphene is a promising candidate for use in gas sensing applications related to the monitoring of dissolved gases in transformer oils. Full article

This study addresses the efficiency and cost challenges of hydrogen evolution reaction (HER) catalysts in the context of carbon neutrality strategies by employing a synergistic approach that combines cation vacancy anchoring and transition metal doping on two-dimensional (2D) MXenes. Using an in situ LiF/HCl etching process, the aluminum layers in Ti₃AlC₂ were precisely removed, resulting in a few-layer Ti₃C₂T_x MXene with an increased interlayer spacing of 12.3 Å. Doping with the transition metals Fe, Co, Ni, and Cu demonstrated that Fe@Ti₃C₂ provided the optimal HER performance, characterized by an overpotential (η₁₀) of 81 mV at 10 mA cm⁻², a low Tafel slope of 33.03 mV dec⁻¹, and the lowest charge transfer resistance (R_ct = 5.6 Ω cm²). Mechanistic investigations revealed that Fe’s 3d⁶ electrons induce an upward shift in the d-band center of MXene, improving hydrogen adsorption free energy and reducing lattice distortion. This research lays a solid foundation for the design of non-precious metal catalysts using MXenes and highlights future avenues in bimetallic synergy and scalability. Full article

A three-dimensional Bi-enriched Bi₂O₃/Bi₂MoO₆ Z-scheme heterojunction photocatalyst was successfully synthesized via a facile one-step hydrothermal method for efficient phenol degradation under visible light. Structural and morphological characterizations (SEM, TEM, and XRD) confirmed the formation of a nanoflower-like architecture with a high specific surface area of 81.27 m²/g. Optical and electrochemical analyses revealed efficient charge separation and extended visible-light response. Under visible-light irradiation (λ > 420 nm), this heterojunction (Bi₂O₃:Bi₂MoO₆ = 3:7) demonstrated exceptional performance, degrading 97.06% of phenol (30 mg/L) within 60 min. XPS analysis confirmed the Z-scheme charge transfer mechanism: Photogenerated electrons in the conduction band of Bi₂O₃ (−0.59 eV) facilitated the generation of ·O₂⁻ radicals, while holes in the valence band of Bi₂MoO₆ (2.44 eV) predominantly produced ·OH radicals. This synergistic effect resulted in highly efficient mineralization and degradation of phenol. Full article

Graphitic carbon nitride (g-C₃N₄) is emerging as one of the most promising non-metallic semiconductors for the degradation of pollutants in water by photocatalytic processes. Its exceptional reduction–oxidation (redox) potentials and adequate band gap of approximately 2.7 eV give it the ability to absorb in the visible light range. However, the characteristic sensitivity to light absorption is limited, leading to rapid recombination of electron–hole pairs. Therefore, different strategies have been explored to optimize this charge separation, among which the formation of heterostructures based on g-C₃N₄ is highlighted. This review addresses recent advances in photocatalysis mediated by g-C₃N₄ heterostructures, considering the synthesis methods enabling the optimization of the morphology and active interface of these materials. Next, the mechanisms of charge transfer are discussed in detail, with special emphasis on type II, type S, and type Z classifications and their influence on the efficiency of photodegradation. Subsequently, the progress in the application of these photocatalysts for the degradation of water pollutants, such as toxic organic dyes, pharmaceutical pollutants, pesticides, and per- and polyfluoroalkyl substances (PFAS), are analyzed, highlighting both experimental advances and remaining challenges. Finally, future perspectives oriented towards the optimization of heterostructures, the efficiency of synthesis methods, and the practical application of these in photocatalytic processes for environmental remediation. Full article

LK-99, with chemical formula Pb_10−xCu_x(PO₄)₆O, was recently reported to be a room-temperature superconductor. While this claim has met with little support in a flurry of ensuing work, a variety of calculations (mostly based on density-functional theory) have demonstrated that the system possesses some unusual characteristics in the electronic structure, in particular flat bands. We have established previously that within DFT, the system is insulating with many characteristics resembling the classic cuprates, provided the structure is not constrained to the P3(143) symmetry nominally assigned to it. Here we describe the basic electronic structure of LK-99 within self-consistent many-body perturbative approach, quasiparticle self-consistent GW (QSGW) approximation and their diagrammatic extensions. QSGW predicts that pristine LK-99 is indeed a Mott/charge transfer insulator, with a bandgap gap in excess of 3 eV, whether or not constrained to the P3(143) symmetry. When Pb₉Cu(PO₄)₆O is hole-doped, the valence bands modify only slightly, and a hole pocket appears. However, two solutions emerge: a high-moment solution with the Cu local moment aligned parallel to neighbors, and a low-moment solution with Cu aligned antiparallel to its environment. In the electron-doped case the conduction band structure changes significantly: states of mostly Pb character merge with the formerly dispersionless Cu d state, and high-spin and low spin solutions once again appear. Thus we conclude that with suitable doping, the ground state of the system is not adequately described by a band picture, and that strong correlations are likely. Irrespective of whether this system class hosts superconductivity or not, the transition of Pb₁₀(PO₄)₆O from being a band insulator to Pb₉Cu(PO₄)₆O, a Mott insulator, and multi-determinantal nature of doped Mott physics make this an extremely interesting case-study for strongly correlated many-body physics. Full article

In this study, density functional theory (DFT) was used to analyze the processes that govern the interactions among triethylaluminum (TEAL), the Ziegler–Natta (ZN) catalyst, and the inhibitory compounds dimethylamine (DMA) and diethylamine (DEA) during olefin polymerization. The structural and charge characteristics of these inhibitors were examined through steric maps and DFT calculations. Combined DFT calculations (D3-B3LYP/6-311++G(d,p)) and IR spectroscopic analysis show that the most efficient way to deactivate the ZN catalyst is via the initial formation of the TEAL·DMA complex. This step has a kinetic barrier of only 27 kcal mol⁻¹ and a negative ΔG, in stark contrast to the >120 kcal mol⁻¹ required to form TEAL·DEA. Once generated, TEAL·DMA adsorbs onto the TiCl₄/MgCl₂ cluster with adsorption energies of −22.9 kcal mol⁻¹ in the gas phase and −25.4 kcal mol⁻¹ in n-hexane (SMD model), values 5–10 kcal mol⁻¹ more favorable than those for TEAL·DEA. This explains why, although dimethylamine is present at only 140 ppm, its impact on productivity (−19.6%) is practically identical to that produced by 170 ppm of diethylamine (−20%). The persistence of the ν(Al–N) band at ~615 cm⁻¹, along with a >30% decrease in the Al–C/Ti–C bands between 500 and 900 cm⁻¹, the downward shift of the N–H stretch from ~3300 to 3200 cm⁻¹, and the +15 cm⁻¹ increase in ν(C–N) confirm Al←N coordination and blockage of alkyl transfer, establishing the TEAL·DMA → ZN pathway as the dominant catalytic poisoning mechanism. Full article

When a semiconducting sample is illuminated by an intensity-modulated monochromatic light beam with photon energy exceeding the band gap, part of the absorbed energy is directly converted into heat through photon–lattice interactions. This gives rise to a heat source that closely follows the temporal profile of the optical excitation, known as the fast heat source. Simultaneously, another portion of the absorbed energy is used to generate electron-hole pairs. These charge carriers diffuse together and recombine via electron–electron and electron–hole interactions, transferring their kinetic energy to the lattice and producing additional heating of the sample. This indirect heating mechanism, associated with carrier recombination, is referred to as the slow heat source. In this study, we develop a model describing surface temperature variations on the non-illuminated side of a thermally thin semiconductor exposed to a rectangular optical pulse, explicitly accounting for the contribution of surface charge carrier recombinations. Using this model, we investigate the influence of surface recombination velocity and the material’s plasma properties on the time-domain temperature response for both plasma-opaque and plasma-transparent samples. Our results demonstrate that charge carrier recombinations can significantly affect the transient photoacoustic signal recorded using a minimum volume cell, highlighting the potential of time-resolved photoacoustic techniques for probing the electronic properties of semiconductors. Full article

One-dimensional TiO₂ nanotube arrays (TNAs) were vertically aligned and obtained via the electrochemical anodization method. In this study, Bi₂S₃-TiO₂-SiO₂/TNA heterojunction photocatalysts were successfully prepared with different amounts of Bismuth(III) sulfide (Bi₂S₃) loading on the TNAs by the successive ionic layer adsorption and reaction (SILAR) method and characterized by X-ray diffraction (XRD) patterns, field-emission scanning electron microscope–energy-dispersive spectroscopy (FESEM-EDS), Fourier transform infrared (FTIR) spectra, ultraviolet-visible diffuse reflectance spectra (UV–Vis/DRS), and electrochemical impedance spectroscopy (EIS) techniques. The photocatalytic performances of the samples were investigated by degrading Basic Yellow 28 (BY 28) under visible-light irradiation. Optimization of the condition using the response surface methodology (RSM) and central composite rotatable design (CCRD) technique resulted in the degradation of BY 28 dye, showing that the catalyst with 9.6 mg/cm² (designated as Bi₂S_3(9.6)-TiO₂-SiO₂/TNA) showed the maximum yield in the degradation process. The crystallite size of about 17.03 nm was estimated using the Williamson–Hall method. The band gap energies of TiO₂-SiO₂/TNA and Bi₂S_3(9.6)-TiO₂-SiO₂/TNA were determined at 3.27 and 1.87 eV for the direct electronic transitions, respectively. The EIS of the ternary system exhibited the smallest arc diameter, indicating an accelerated charge transfer rate that favors photocatalytic activity. Full article

Chemiresistive gas sensors have gained significant attention and have been widely applied in various fields. However, the gap between experimental observations and fundamental sensing mechanisms hinders systematic optimization. Despite the critical role of modeling in explaining atomic-scale interactions and offering predictive insights beyond experiments, existing reviews on chemiresistive gas sensors remain predominantly experimental-centric, with a limited systematic exploration of the modeling approaches. Herein, we present a comprehensive overview of the modeling approaches for chemiresistive gas sensors, focusing on two critical processes: the reception and transduction stages. For the reception process, density functional theory (DFT), molecular dynamics (MD), ab initio molecular dynamics (AIMD), and Monte Carlo (MC) methods were analyzed. DFT quantifies atomic-scale charge transfer, and orbital hybridization, MD/AIMD captures dynamic adsorption kinetics, and MC simulates equilibrium/non-equilibrium behaviors based on statistical mechanics principles. For the transduction process, band-bending-based theoretical models and power-law models elucidate the resistance modulation mechanisms, although their generalizability remains limited. Notably, the finite element method (FEM) has emerged as a powerful tool for full-process modeling by integrating gas diffusion, adsorption, and electronic responses into a unified framework. Future directions highlight the use of multiscale models to bridge microscopic interactions with macroscopic behaviors and the integration of machine learning, accelerating the iterative design of next-generation sensors with superior performance. Full article

Nanomaterials with large specific surface area (SSA) have emerged as pivotal platforms for energy storage and environmental remediation, primarily due to their enhanced active site exposure, improved mass transport capabilities, and superior interfacial reactivity. Among them, polymeric carbon nitride (g-C₃N₄) has garnered significant attention in energy and environmental applications owing to its visible-light-responsive bandgap (~2.7 eV), exceptional thermal/chemical stability, and earth-abundant composition. However, the practical performance of g-C₃N₄ is fundamentally constrained by intrinsic limitations, including its inherently low SSA (<20 m²/g via conventional thermal polymerization), rapid recombination of photogenerated carriers, and inefficient charge transfer kinetics. Notably, the theoretical SSA of g-C₃N₄ reaches 2500 m²/g, yet achieving this value remains challenging due to strong interlayer van der Waals interactions and structural collapse during synthesis. Recent advances demonstrate that state-of-the-art strategies can elevate its SSA to 50–200 m²/g. To break this surface area barrier, advanced strategies achieve SSA enhancement through three primary pathways: pre-treatment (molecular and supramolecular precursor design), in process (templating and controlled polycondensation), and post-processing (chemical exfoliation and defect engineering). This review systematically examines controllable synthesis methodologies for high-SSA g-C₃N₄, analyzing how SSA amplification intrinsically modulates band structures, extends carrier lifetimes, and boosts catalytic efficiencies. Future research should prioritize synergistic multi-stage engineering to approach the theoretical SSA limit (2500 m²/g) while preserving robust optoelectronic properties. Full article