Surface Electronic Properties Research Articles

First principles investigations on structural, electronic, optical, and thermodynamical properties of bulk and surfaces of In2CO

This study reports first-principles investigations of the structural, electronic, thermal, and optical properties of a novel material In2CO in bulk phase and slab models in (001), (100), (101), and (011) orientations to develop a fundamental understanding of its characteristics. The material appeared structurally as well as dynamically stable in the orthorhombic phase. The thermal properties demonstrated that the material's heat capacity is more temperature-sensitive than entropy and enthalpy. The electronic band structure analysis revealed that the orthorhombic phase material is a semiconductor with a narrow indirect band gap. The electronic structures modeled using the spin-orbit coupling yielded the metallic phase of the slabs except for (001) orientation. The electromagnetic absorption characteristics of the compound are also investigated to explore the material's potential in optoelectronic applications. The direction-dependent study of optical characteristics revealed that the (001) slab of the material can be an efficient infrared detector. The survey findings provide instrumental outcomes in utilizing In2CO in electronic and optoelectronic applications.

Enhancing electrode efficiency by tuning surface electronic properties and defects in NiFe layered double hydroxide nanosheets with Al or Zn cation vacancies

Layered double hydroxides (LDHs) containing transition metals have emerged as promising electrode materials for supercapacitors due to their low cost, strong redox activity, and environmental friendliness. In this study, we propose a novel approach by creating Zn-defect Zn(II) engineered D-NiFeZn-LDHs through cyclic voltammetry etching in an alkaline solution of NiFeZn-LDHs synthesized on a carbon cloth substrate. This defect engineering increases electrochemical active sites and improves ion diffusion within the layered structure. The D-NiFeZn-LDHs demonstrate an impressive specific capacitance of 1204.8 F g⁻1 at 1 A g⁻1 and retain 61.52 % of their initial capacity after 10,000 cycles at 10A g⁻1, showcasing excellent long-term cycling stability. Moreover, the all-solid-state asymmetric supercapacitor constructed using D-NiFeZn-LDHs delivers a high energy density of 31.63 Wh kg⁻1 at 125 W kg⁻1 and retains 65.95 % of its capacity after 5000 cycles at a high current density of 10 A g⁻1. These findings provide a new strategy for developing high-performance energy storage materials.

Dopant effects on the environment-dependent chemical properties of NiO(100) surfaces

NiO is a promising material for applications such as electronic devices and catalysts due to its low cost, environmental friendliness, and optimal chemical and electronic properties. Inclusion of a dopant element into the NiO near surface structure can further tune material properties. Despite extensive studies on doped NiO (M−NiO) materials, there remains a lack of knowledge regarding the connection between dopant, environment-dependent dominant near surface structures, and overall chemical properties. Here, the dopant effects on the near surface structure and electronic properties on M−NiO(100) are systematically examined using a combination of density functional theory (DFT) and ab initio phase diagrams. The simultaneous factors tested include dopant element (Al, Mo, Nb, Sn, Ti, V, W, or Zr), dopant placement (surface or subsurface), Ni/O vacancies (surface or subsurface), and oxygen species (O* or O2*) adsorption. The results reveal the dominant structures and compositions of M−NiO(100) under a wide range of environmental conditions (i.e. varying temperature and pressure). Subsequent electronic analyses of the dominant M−NiO(100) structures shows non-uniform changes in charge redistribution, band gap, work function, and d-band center with dopant and near surface structure, emphasizing the role of dopants in tuning M−NiO(100) both geometric and electronic properties. Overall, these multiscale modeling results enable a rapid, effective, and a priori prediction of dominant M−NiO(100) structures with distinct chemical properties, crucial for guiding NiO-based materials design with enhanced performance for advanced electronics, energy storage, and catalytic systems.

G-C3N4 coupled with GO accelerates carrier separation via high conductivity for photocatalytic MB degradation

Graphitic carbon nitride (g-C3N4) is widely utilized in photocatalysis due to its responsiveness to visible light, low cost, and non-toxicity. However, its efficiency is limited by factors such as the rapid recombination of photogenerated electron-hole pairs, slow electron transfer rates, and a limited number of active surface sites. In this study, g-C3N4 was synthesized through thermal polymerization, and varying amounts of graphene oxide (GO) were incorporated via physical blending to fabricate composite photocatalysts. The results indicated that the incorporation of GO not only increased the specific surface area and modified the pore size distribution of g-C3N4 but also affected the heptazine ring structure through chemical bonding, thereby enhancing the density of active sites. Photocatalytic degradation experiments with methylene blue (MB) indicated that g-C3N4 containing 2% GO exhibited photocatalytic activity 2.84 times greater than that of pristine g-C3N4. Kinetic simulations indicated that the Kapp value for the 2% GO-g-C3N4 composite was 0.00469min-1, which is 4.34 times higher than that of pure g-C3N4 (0.00108min-1). Furthermore, this composite maintained high photocatalytic activity after four cycles of reuse. An analysis of the photocatalytic degradation mechanism revealed that the incorporation of GO effectively promoted the separation and transfer of photogenerated electron-hole pairs, enhanced photocurrent density, and improved carrier separation efficiency. Electron spin resonance (ESR) and free radical scavenging experiments confirmed that the primary active species involved in the degradation of MB by the composite photocatalyst were ·O2- and h+. This study presents a novel approach for enhancing the photocatalytic performance of g-C3N4 by modifying its electronic structure and surface properties.

Electronic structure of biochar modified through self-doping with boron, nitrogen and sulfur atoms for rapid and efficient adsorption of COVID-19 drug residues

Self-doping of biochar with various heteroatoms can significantly modify its electronic structure and surface properties, thereby enhancing its adsorption capacity. Allium mongolicum Regel (AM) was a desert herb known for hyperaccumulating boron and possessing a cavity structure. AMAC-3 derived from the pyrolysis of AM, exhibited a high specific surface area (2754 cm2g−1), a larger pore volume (2.513 cm3g−1), an appropriate degree of graphitization (IG/ID = 0.99), and a certain content of heteroatoms (boron, nitrogen and sulfur). AMAC-3 achieved equilibrium adsorption of 20 mg L−1COVID-19 drugs residues within 5–8 min, with equilibrium adsorption capacity ranging from 158 to 195mg g−1 and the drug removal rate between 79 % and 98 %. Furthermore, AMAC-3 maintained high adsorption efficiency in the presence of coexisting anions and spiked real water samples. The shorter adsorption equilibrium time and higher removal rate of AMAC-3 were attributed to the rapid mass transfer in the 3D pores, as well as the rapid binding of more electrons. Boron was the preferred binding site for heteroatom sites due to its electron deficient nature. This study offered insights into the utilization of self-doped heteroatoms for modulating the electronic structure of adsorbent, thereby reducing adsorption equilibrium time and enhancing removal efficiency.

Fermi Arcs Dominating the Electronic Surface Properties of Trigonal PtBi2

AbstractMaterials combining topologically non‐trivial behavior and superconductivity offer a potential route for quantum computation. However, the set of available materials intrinsically realizing these properties are scarce. Recently, surface superconductivity has been reported in PtBi2 in its trigonal phase and an inherent Weyl semimetal phase has been predicted. Here, based on scanning tunneling microscopy experiments, the signature of topological Fermi arcs are revealed in the normal state patterns of the quasiparticle interference. It is shown that the scattering between Fermi arcs dominates the interference spectra, providing conclusive evidence for the relevance of Weyl fermiology for the surface electronic properties of trigonal PtBi2.

Dispersion and self-assembly of 2,5-dimercapto-1,3,4-thiadiazole (DMTD) functionalized silver QDs in 6 CHBT liquid crystal

ABSTRACT Silver nanoparticles were synthesised using silver nitrate and tri-sodium citrate and were functionalized with 2,5-Dimercapto-1,3,4-thiadiazole (DMTD) linking molecules. Functionalized silver nanoparticles dispersed within 4-(trans-4-n hexylcyclohexyl) isothiocyanatobenzoate (6CHBT) liquid crystal (LC) matrices have attracted significant attention because of their potential for tailoring tuneable surface plasmonic, optical, and electronic properties by controlling the self-assembly of silver dots. The unique combination of functionalized nanoparticles and 6CHBT LCs offers a versatile platform for manipulating interactions at the nanoscale. The dispersion of functionalized Ag nanoparticles within the LCs appears to substantially modify the plasmonic and opto-electronic properties of the Ag QDs. The formation and morphology of the self-assembled structures of silver nanoparticles were confirmed by Optical and Scanning Electron Microscopy. Optical microscopy (OM) and Scanning Electron Microscopy (SEM) images of Ag-doped 6CHBT confirmed the formation of nano-micro spheres, as well as ring and rod-like structures in LC media. We have used High-Resolution X-ray diffraction (HR-XRD), Fourier-Transform Infrared Spectroscopy (FTIR), Surface-Enhanced Raman Spectroscopy (SERS), Optical Microscopy (OM), Scanning Electron Microscopy (SEM), Ultraviolet-visible-near-infrared Spectroscopy (UV-Vis-NIR), and Fluorescence (FL) Spectroscopy. We calculated the electronic properties such as the bandgap of the synthesised Ag QDs and functionalized Ag QDs using UV-Vis-NIR and Tauc’s plot curves. Surface-enhanced Raman spectroscopy, Optical microscopy, SEM, and UV-Vis-NIR spectral data were used to correlate the properties of the LC and QDs hybrid systems.

Engineering of in-plane SnS2–SnO2 nanosheets heterostructures for enhanced H2S sensing

In-plane heterostructures has attracted considerable interest due to exceptional electron transport properties, high specific surface area, and abundant active sites. However, synthesis of in-plane SnS2–SnO2 heterostructures are rarely reported, and the deep investigation of the fine structure on reactivity is of great significance. Here, we propose partial in-situ oxidation strategy to construct the in-plane SnS2–SnO2 heterostructures and the surface properties, the ratio of two components can be finely tuned by precisely adjusting the treatment temperature. In particular, the SnS2–SnO2 heterostructures formed after annealing of SnS2 nanosheets at 350 °C exhibits a unique electronic structure and surface properties due to rich grain boundaries, which exhibits excellent gas sensing performance to H2S (Ra/Rg = 169.81 for 5 ppm H2S at 160 °C, fast response and recovery dynamic (41/101 s), excellent reliability (σ = 0.01) and sensing stability (φ = 0.11 %)). Notably, the in-plane heterostructures endow the material with abundant grain boundaries and effectively regulates the electronic structure of the Sn p-orbital, which facilitate the formation of active oxygen species (O−(ad)), thus contributing to the sensing performance. Our work provides a promising platform to design in-plane heterostructures for various advanced applications.

Vanadium doped in-plane 1T-2H molybdenum disulfide heterostructure as efficient electrocatalyst for lithium-sulfur batteries

The active electronic states in 1T-MoS2 are highly desirable for catalyzing polysulfides conversion. However, stable 1T-MoS2 is difficult to produce using common approaches. Herein, V uniformly doped in-plane 1T-2H heterostructured MoS2 nanosheets (V-MoS2) are prepared by a facile hydrothermal method with a polyoxometalate precursor containing periodic Mo and V atomic arrangement. The doping of V induces the phase transition from semiconducting 2H-MoS2 to metallic 1T-MoS2 and stabilizes the resulted 1T phase. Importantly, the incorporation of V not only modifies the surface electronic property of MoS2, enhancing the active site density, but also improves the adsorption of polysulfides and the catalytic efficiency for sulfur redox reactions. With these advantages, the Li-S batteries using V-MoS2 electrocatalyst achieve accelerated reaction kinetics and superior electrochemical performance. When the S loading of the cathode is 5.41 mg cm−2, a favorable discharge capacity of 4.98 mAh cm−2 is obtained with satisfying cycle stability. This work provides an efficient atomic engineering approach for the design of high performance electrocatalyst for Li-S batteries.

Recent Advances in Engineering of 2D Layered Metal Chalcogenides for Resistive-Type Gas Sensor.

2D nanomaterials have triggered widespread attention in sensing applications. Especially for 2D layered metal chalcogenides (LMCs), the unique semiconducting properties and high surface area endow them with great potential for gas sensors. The assembly of 2D LMCs with guest species is an effective functionalization method to produce the synergistic effects of hybridization for greatly enhancing the gas-sensing properties. This review starts with the synthetic techniques, sensing properties, and principles, and then comprehensively compiles the advanced achievements of the pristine 2D LMCs gas sensors. Key advances in the development of the functionalization of 2D LMCs for enhancing gas-sensing properties are categorized according to the spatial architectures. It is systematically discussed in three aspects: surface, lattice, and interlayer, to comprehend the benefits of the functionalized 2D LMCs from surface chemical effect, electronic properties, and structure features. The challenges and outlooks for developing high-performance 2D LMCs-based gas sensors are also proposed.

Insights into the Effect of a Microwave Field on the Properties of Modified γ-Alumina: A DFT Study

γ-Alumina is often used as a support for hydrodesulfurization catalysts due to its excellent performance. During the catalytic reaction, the strong surface acidity of γ-alumina can induce a strong interaction between the active phase and the support. The reaction activity of the catalyst can be affected by changing the present mode of the active phase on the surface of the support. The (110) crystal plane, acting as the strongest acidity plane of γ-alumina, was selected for modification. The supports modified with boron and phosphorus were successfully constructed, and the acid strengths were quantified by simulating the adsorption of the relevant probe molecules: pyridine in correlation with surface electronic properties via density functional theory. The surface adsorption energy calculation shows that the boron-modified surface is able to moderately reduce the adsorption capacity of alumina, while that of the surface modified by phosphorus is found to be enhanced over the sites of a tetrahedral coordination structure; however, at the other unsaturated Al sites, this is obviously reduced. The results of introducing electric fields imply that applying horizontal electric fields changes the surface acidity of alumina under the premise of a stable structure. With the enhancement of the horizontal electric fields, the adsorption capacity of tetra-coordination sites on the original surface gradually decreases, while those of the others gradually increases. However, for the boron-modified surface, introducing horizontal electric fields can reduce the adsorption capacity of all sites. Hence, microwave-electric-field-assisted modification of B further reduces the surface acidity of alumina, making it beneficial for deep hydrodesulfurization reactions.

Aminotriazine derived N-doped mesoporous carbon with a tunable nitrogen content and their improved oxygen reduction reaction performance.

The electrocatalytic activity of carbon materials is highly dependent on the controlled modulation of their composition and porosity. Herein, mesoporous N-doped carbon with different amounts of nitrogen was synthesized through a unique strategy of using a high nitrogen containing CN precursor, 3-amino 1,2,4 triazine (3-ATZ) which is generally used for the preparation of carbon nitrides, integrated with the combination of a templating method and high temperature treatment. The nitrogen content and the graphitisation of the prepared materials were finely tuned with the simple adjustment of the carbonisation temperature (800-1100 °C). The optimised sample as an electrocatalyst for oxygen reduction reaction (ORR) exhibited an onset potential of 0.87 V vs. RHE with a current density of 5.1 mA cm-2 and a high kinetic current density (Jk) of 33.1 mA cm-2 at 0.55 V vs. RHE. The characterisation results of the prepared materials indicated that pyridinic and graphitic nitrogen in the carbon framework promoted ORR activity with improved four-electron selectivity and excellent methanol tolerance and stability. DFT calculations demonstrated that the structural and planar defects in the N-doped carbon regulated the surface electronic properties of the electrocatalyst, leading to a reduction in the energy barrier for the ORR activity. This strategy has the potential to unlock a platform for designing a series of catalysts for electrochemical applications.

Effect of Ni substitution atom on electronic properties and surface oxidation of pyrrhotite

The crystal and surface electronic properties of minerals are fundamentally linked to their flotation behavior. To investigate the effects of Ni substitution for Fe in pyrrhotite on the crystal and surface properties, as well as its oxidation by O2, density functional theory (DFT) was employed to analyze these changes at a microscopic level in both monoclinic and hexagonal pyrrhotite. The findings reveal that Ni substitution increases electron activity in monoclinic pyrrhotite, enhancing its resistance to oxidation by O2, while also strengthening the interaction between Ni-substituted monoclinic pyrrhotite and butyl xanthate. Conversely, in hexagonal pyrrhotite, Ni substitution enhances electron stability but makes it more susceptible to oxidation by O2 and weakens its interaction with butyl xanthate. Understanding the electronic properties and interaction mechanisms of Ni-substituted pyrrhotite with O2 is crucial for elucidating the surface oxidation mechanisms of pyrrhotite. This research offers insights and guidance for optimizing pyrrhotite flotation processes.

Construction of ZnAl LDH-Derived Sulfides with Etching Modification to Trigger Photocatalytic H2 Production and Degradation Oxidation.

Constructing novel functional photocatalysts represents a promising approach to optimize the energy band structure and facilitate the separation of photogenerated carriers. Layered double hydroxides (LDHs) exhibit notable advantages in photocatalysis due to the exceptional photoelectrochemical properties and elevated number of active surface atoms. However, an unsuitable band gap and limited carrier migration have inhibited their development in photocatalysis. Herein, we propose a novel in situ topological vulcanization strategy for optimizing the photocatalytic activity of ZnAl LDH-derived sulfides (ZnAlSx). The subsequent etching process via a 1 M NaOH solution was introduced to construct the ZnSx photocatalysts. Then, the crystallinity of the crystals was enhanced by etching to further improve the catalytic activity and stability of ZnSx. The as-synthesized ZnSx shows an excellent photocatalytic hydrogen production rate (11.89 mmol/g/h) and tetracycline degradation efficiency (91.94%) under light illumination, and its hydrogen evolution efficiency is approximately 176 and 2 times greater than that of ZnAl LDH and ZnAlSx, respectively. The characterization and density functional theory (DFT) analysis confirmed that the surface electronic properties and energy band structure of ZnAl LDH were significantly optimized after experimental treatment, resulting in enhanced carrier separation and photooxidative reduction capacity. Combining in situ topological vulcanization and etching to realize the functional conversion of ZnAl LDH provides promising insights into the construction of high-performance, low-cost photocatalysts.

Electronic Properties of Atomic Layer Deposited HfO2 Thin Films on InGaAs Compared to HfO2/GaAs Semiconductors

This paper demonstrates how the treatment of III-V semiconductor surface affects the number of defects and ensures the conformal growth of the high-k dielectric thin film. We present the electrical properties of an HfO2/InGaAs-based MOS capacitor, in which growth temperatures and surface treatments of the substrate are two key factors that contribute to the uniformity and composition of the HfO2 thin films. A remarkable asymmetry observed in capacitance versus voltage measurements was linked to the interface defects and charge redistribution, as confirmed from X-ray photoelectron spectroscopy. The GaAs substrates that were etched with only NH4OH showed a large frequency dispersion and a higher surface roughness; however, the HfO2 thin films grown on GaAs pre-treated with both NH4OH etching and (NH4)2S passivation steps produced a desirable surface and superior electronic properties.

(Invited) Advanced Electronic Characterization of Wide Band Gap Semiconductor Defects at the Nanoscale

Wide bandgap materials such as gallium nitride (GaN) and gallium oxide (Ga2O3) are currently under development for realizing next-generation high power electronic devices beyond silicon. Vertical structures produced through homoepitaxial growth are preferred for scaling high-voltage devices, which places strict demands on the quality of bulk substrates. In particular, extended defects can propagate during epitaxial growth into the active areas of devices. Therefore, there is a need for identifying defects and determining their electronic properties at relevant nano- to micro- scale dimensions in order to disentangle their combined effects on macroscopic devices. Here, we use a combination of laser-based photoemission electron microscopy (PEEM) and electrical atomic force microscopy (AFM) methodologies to investigate the local electronic properties of surface defects in epitaxially grown GaN and β-Ga2O3. PEEM is a non-scanning electron microscopy technique where photoelectrons emitted by a surface illuminated by deep-ultraviolet light are imaged with nanometer-scale spatial resolution. The emitted photoelectrons are sensitive to the local electronic structure, making PEEM a powerful tool for evaluating electronic changes at length scales relevant for devices, and provides valuable information for identifying “killer” defects which must be minimized during device growth and processing.The difficulty in producing large, low dislocation density bulk GaN substrates has led to longstanding issues with leakage current in diodes and transistor devices. We identify surface defects with different electronic properties in GaN epitaxy on different substrates using PEEM. We observe star-shaped defects on strain-patterned GaN substrates and elongated dark patches on growth ridges on ammonothermally grown GaN substrates. In both cases, the observed electronic changes in PEEM correlate directly with local electrical AFM measurements, revealing that local changes in the electronic structure at these defects results in altered electrical conduction.In contrast, the development of large bulk Ga2O3 substrates has been more successful, yet the identification and influence of various defects on device performance is still largely unknown at this point. The topography of β-Ga2O3 epitaxy varies widely between growth methods and substrate orientations. For example, β-Ga2O3 by hydride vapor physical epitaxy lacks fine structure, yet has surface defects that regularly appear in parallel orientations. In β-Ga2O3 grown on different substrate orientations, we observe variations in the surface electronic properties using PEEM. For certain substrate orientations and growths, we find nanoscale variations in doping, while other orientations display micron-scale electronic inhomogeneity and defects. Our results demonstrate that laser-based PEEM can be a powerful tool for detecting electrically active defects, as well as evaluating the nanoscale electronic homogeneity of wide bandgap semiconductors.

Development of Bifunctional Electrocatalyst for Overall Water Electrolysis: Vanadium and Phosphorus Dual-Doping Strategy on Ni3S2 Nanoneedle

Along with the rapid consumption of fossil fuels and serious environmental pollution, the development of renewable and clean energy has been receiving a lot of attention recently. Among the various renewable energy sources, hydrogen (H2) is considered as most promising substance in future energy society owing to its high gravimetric energy density and environmental friendliness. Electrochemical water electrolysis system is powerful strategy for high-purity hydrogen production without emission of any pollutants. It consists of two electrocatalytic reactions: oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). However, the practical efficiency of water electrolysis is limited due to the intrinsically sluggish reaction kinetics of OER and HER. To date, the precious metal-based electrocatalysts such as RuO2 and Pt/C for OER and HER, respectively, were employed as state-of-the-art electrocatalyst to enhance the performance of water electrolysis. However, due to the high expense, mono-functionality, and unsatisfactory stability of the precious metal-based materials, research on bifunctional electrocatalysts with low cost and high activity has become an urgent topic. To date, numerous scientific endeavors have been dedicated to the advancement of highly efficient non-noble metal-based bifunctional electrocatalysts such as transition metal oxides, hydroxides, sulfides, carbides, nitrides, and phosphides. Among these, Ni3S2 has emerged as a particularly promising electrocatalyst for water splitting, garnering substantial attention owing to its high electric conductivity, rich redox property, abundance in the Earth's crust, and environmentally friendly characteristics. Nevertheless, the electrocatalytic activity of Ni3S2 lags behind that of noble metal counterparts. Therefore, elaborate modification of Ni3S2 catalyst should be conducted to further improve its intrinsic activity toward OER and HER. Among the various strategies, heteroatom doping into Ni3S2 structure could be adopted as powerful technique for enhancement of electrocatalytic performance. The homogeneously incorporated dopants not only generate lattice disorders but elaborately modulate the surface electronic property. Specifically, high-valent cation dopants such as vanadium and molybdenum can effectively mediate the change of chemical states of Ni active sites during the step-wise electrocatalytic procedure. Meanwhile, additionally introduced anion dopants, which have lower electronegativity compared with sulfur, can reduce the electron trapping phenomenon induced by excessive electron transfer from nickel to sulfur. Inspired by above features, we synthesized V and P co-doped Ni3S2 nanoneedles directly grown on nickel foam (V-Ni3S2-P/NF) through facile two-step preparation method. First, V doped Ni3S2 nanoneedles were homogeneously grown on NF (V-Ni3S2/NF) by hydrothermal process without use of nickel precursor. The vanadium ions promote the nucleation of Ni3S2 species and lead the preferential growth toward 1D direction during the hydrothermal reaction. After that, the V-Ni3S2/NF was annealed in the tube furnace with the NaH2PO2 as a phosphorus precursor under the Ar flow. Under the mild annealing condition, the PH3 gases generated from thermal decomposition of NaH2PO2 reacted with the V-Ni3S2 species. Consequently, the V-Ni3S2 was partially phosphidated into V-Ni3S2-P throughout anion exchange process. As a result, the V-Ni3S2-P/NF electrocatalyst exhibited excellent bifunctional activity toward both OER and HER compared with mono-doped and un-doped counterparts and precious metal-based electrocatalysts. Furthermore, the outstanding electrocatalytic performance of V-Ni3S2-P/NF was well-maintained over the 100 h of continuous operation under alkaline condition. This study will contribute to the development of efficient and cost-effective electrocatalysts for future energy conversion and storage technologies.

First-Principles Insights into Highly Sensitive and Reusable MoS2 Monolayers for Heavy Metal Detection.

This study explores the potential of MoS2 monolayers as heavy metal sensors for As, Cd, Hg, and Pb using density functional theory (DFT) and Non-Equilibrium Green's Function (NEGF) simulations. Our findings reveal that As and Pb adsorption significantly alters the surface structure and electronic properties of MoS2, introducing impurity levels and reducing the band gap. Conversely, Cd and Hg exhibit weaker interactions with the MoS2 surface. The MoS2 monolayer sensors demonstrate exceptional sensitivity for all four target heavy metals, with values reaching 126,452.28% for As, 1862.67% for Cd, 427.71% for Hg, and 83,438.90% for Pb. Additionally, the sensors demonstrate selectivity for As and Pb through distinct response peaks at specific bias voltages. As and Pb adsorption also induces magnetism in the MoS2 system, potentially enabling magnetic sensing applications. The MoS2 monolayer's moderate adsorption energy facilitates rapid sensor recovery at room temperature for As, Hg, and Cd. Notably, Pb recovery time can be significantly reduced at elevated temperatures, highlighting the reusability of the sensor. These results underscore the potential of MoS2 monolayers as highly sensitive, selective, and regenerable sensors for real-time heavy metal detection.

Exploring Ti active sites in Ziegler-Natta catalysts through realistic-scale computer simulations with universal neural network potential

We investigate the interaction dynamics between TiCl4 molecules and a MgCl2 (110) cluster to understand the complexities of Ziegler-Natta catalysts through molecular dynamics simulations. Our study reveals significant distortion of Mg atoms at the edge of cluster, influencing TiCl4 adsorption behavior, cluster stability, and reactivity. Various TiCl4 configurations on the MgCl2 surface, such as octahedral and bridging forms, illustrate the versatility of surface in accommodating different molecular arrangements, affecting catalytic performance. We explore diverse adsorption sites influenced by surface topology and electronic properties, revealing a range of adsorption energies from 15.7 to 29.2 kcal/mol. This indicates a complex interplay of molecular forces, significantly impacting catalytic efficiency at distorted sites. Nudged Elastic Band calculations reveal varied activation energies for ethylene insertion, suggesting faster reaction rates at certain sites and highlighting highly favorable dynamics at Corradini type Ti active sites. All these findings offer new directions for enhancing catalyst performances.

Crystal structure and characterization of monascin from the extracts of Monascus purpureus-fermented rice.

We present a novel solid form of monascin, an azaphilonoid derivative extracted from Monascus purpureus-fermented rice. The crystal structure, C21H26O5, was characterized by single-crystal X-ray diffraction and belongs to the orthorhombic space group P212121. To gain insight into the electronic properties of the short contacts in the crystalline state of monascin, we utilized the Experimental Library of Multipolar Atom Model 2 (ELMAM2) database to transfer the electron density of monascin in its crystalline state. Hirshfeld surface analysis, fingerprint analysis, electronic properties and energetic characterization reveal that intermolecular C-H...O hydrogen bonds play a crucial role in the noncovalent bonding interactions by connecting molecules into two- and three-dimensional networks. The molecular electrostatic potential (MEP) map of the monascin molecule demonstrates that negatively charged regions located at four O atoms are favoured binding sites for more positively charged amino acid residues during molecular recognition. In addition, powder X-ray diffraction confirms that no transformation occurs during the crystallization of monascin.