Stacking Configurations Research Articles

Twisted BiOCl Moiré Superlattices for Photocatalytic Chloride Reforming of Methane.

Solar-driven conversion of CH4 into value-added methyl chlorides and H2 with abundant chloride ions offers a sustainable CH4 reforming strategy but suffers from inefficient Cl- activation and severe e--h+ recombination in traditional photocatalysts. Herein, we demonstrate that BiOCl moiré superlattices with a 11.1° twist angle are highly efficient for photocatalytic CH4 reforming into CH3Cl and H2 with NaCl. These moiré superlattices, featuring misalignment-induced tensile strains, destabilize surface Bi-Cl bonds, facilitating a hole-mediated MvK-analogous process to activate lattice Cl into reactive •Cl for CH4 chlorination. Meanwhile, their twisted stacking configurations reinforce interlayer electronic coupling and thus accelerate out-of-plane carrier transfer. Along with surface anchoring of single-atom Pt sites for H2 evolution, the resulting Pt1/BiOCl moiré superlattices deliver a CH3Cl yield of 53.4 μmol g-1 h-1 with an impressive selectivity of 96% under visible light. This study highlights the potential of lattice engineering in two-dimensional photocatalysts to regulate structural strains and carrier dynamics for the decentralized reforming of CH4.

Magnetic ordering and dynamics in monolayers and bilayers of chromium trihalides: atomistic simulations approach

We analyze magnetic properties of monolayers and bilayers of chromium iodide, \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {CrI}_3$$\\end{document}, in two different stacking configurations: AA and rhombohedral ones. Our main focus is on the corresponding Curie temperatures, hysteresis curves, equilibrium spin structures, and spin wave excitations. To obtain all these magnetic characteristic, we employ the atomistic spin dynamics and Monte Carlo simulation techniques. The model Hamiltonian includes isotropic exchange coupling, magnetic anisotropy, and Dzyaloshinskii-Moriya interaction. As the latter interaction is relatively weak in pristine \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {CrI}_3$$\\end{document}, we consider a more general case, when the Dzyaloshinskii-Moriya interaction is enhanced externally (e.g. due to gate voltage, mechanical strain, or proximity effects). An important issue of the analysis is the correlation between hysteresis curves and spin configurations in the system, as well as formation of the skyrmion textures.

Thermally Induced Irreversible Disorder in Interlayer Stacking of γ-GeSe.

The interlayer stacking shift in van der Waals (vdW) crystals represents an important degree of freedom to control various material properties, including magnetism, ferroelectricity, and electrical properties. On the other hand, the structural phase transitions driven by interlayer sliding in vdW crystals often exhibit thickness-dependent, sample-specific behaviors with significant hysteresis, complicating a clear understanding of their intrinsic nature. Here, the stacking configuration of the recently identified vdW crystal, γ-GeSe, is investigated, and the disordering manipulation of stacking sequence is demonstrated. It is observed that the well-ordered AB' stacking configuration in as-synthesized samples undergoes irreversible disordering upon Joule heating via electrical biasing or thermal treatment, as confirmed by atomic resolution scanning transmission electron microscopy (STEM). Statistical analysis of STEM data reveal the emergence of stacking disorder, with samples subjected to high electrical bias reaching the maximum levels of disorder. The energies of various stacking configurations and energy barriers for interlayer sliding are examined using first-principles calculation and a parameterized model to elucidate the key structural parameters related to stacking shift. The susceptibility of interlayer stacking to disorder through electrical or thermal treatments should be carefully considered to fully comprehend the structural and electrical properties of vdW crystals.

Layer Number and Stacking Engineering of MoS2 Crystals for High-Performance Polarization-Sensitive Photodetector.

The layer and stacking engineering of two-dimensional (2D) transition-metal dichalcogenides (TMDs) gives rise to novel phenomena and multiapplications; thus, TMDs have garnered considerable attention. However, the precisely customized fabrication of stacked 2D materials to date is largely limited to the lack of effective and controllable growth strategies, prone to the unpredictable stacking orders and randomly distributed nucleation sites. Here, we devise an optimized chemical vapor deposition approach for modulating the MoS2 single crystals from monolayer to multilayer with diverse stacking configurations. Significantly, the phototransistor based on monolayer MoS2 single crystal exhibits an ultrasensitive performance with a high photoresponsivity (R) of 3.3 × 104 A W-1 and a remarkable detectivity (D*) of above 1.7 × 1014 Jones at 405 nm light illumination. Ultralow-frequency and angle-resolved polarized Raman spectroscopy is used to systematically uncover the delicate interlayer interactions and crystallographic anisotropy. Moreover, the polarization-sensitive photodetectors using 1-3L MoS2 show a layer number-dependent anisotropic performance, with dichroism ratios of 1.36, 1.44, and 1.52. This work offers a promising method to not only enable the fabrication of new customized layer-, stacking-, and twist-2D materials but also provides the foundation for the development of advanced polarization-sensitive and optoelectronic devices based on stacking transitions.

Correlated topological flat bands in rhombohedral graphite

Flat bands and nontrivial topological physics are two important topics of condensed matter physics. With a unique stacking configuration analogous to the Su-Schrieffer-Heeger model, rhombohedral graphite (RG) is a potential candidate for realizing both flat bands and nontrivial topological physics. Here, we report experimental evidence of topological flat bands (TFBs) on the surface of bulk RG, which are topologically protected by bulk helical Dirac nodal lines via the bulk-boundary correspondence. Moreover, upon in situ electron doping, the surface TFBs show a splitting with exotic doping evolution, with an order-of-magnitude increase in the bandwidth of the lower split band, and pinning of the upper band near the Fermi level. These experimental observations together with Hartree-Fock calculations suggest that correlation effects are important in this system. Our results demonstrate RG as a platform for investigating the rich interplay between nontrivial band topology, correlation effects, and interaction-driven symmetry-broken states.

Smart carbon fiber reinforced plastic tubes with electromechanical structural health self-monitoring system

Carbon fiber-reinforced plastics (CFRPs), are utilized in the various mobilities owing to their superior specific structural rigidity. However, the studies for the structural health monitoring (SHM) of a tubular CFRP are relatively limited compared to its market share although it is directly related to the structural duties. Thus, this study investigated structural health self-monitoring (SHSm) of tubular CFRPs by monitoring their electrical resistances simultaneously. Multiple electrodes monitored electrical resistances of the CFRP tubes in terms of their mechanical deformation realizing condition-based SHM without any sensors. The proposed self-monitoring technology enabled not only local but also global deformation even after the mechanical fractures. Furthermore, the proposed self-monitoring method was comparatively analyzed and verified with corresponding mechanics and finite element analysis. Therefore, real-time SHSm technology for tubular CFRPs with various fiber stacking configurations was realised in this study covering all the deformation types over the whole structures.

Optimization of the Electron Spectrometer Telescope geometry for the PRESET satellite through Monte Carlo simulation

The Electron Spectrometer Telescope (EST) aboard the PRESET satellite mission aims to measure the pitch angle distribution of 0.3–4 MeV electrons in the outer Van Allen belts. The PRESET satellite is planned to launch into a sun-synchronous low Earth orbit in Q2, 2026. We present comprehensive Monte Carlo simulations to optimize the design and response of the EST instrument. The EST consists of a stack of silicon strip detectors and a collimator to take pitch-angle dependent electron spectral measurements with a target angular resolution of 6° while rejecting the proton, heavy ion and gamma detection events. Various collimator designs and detector stacking configurations are investigated using the Geant4 code to deduce an optimal design and configuration. For validation of the Geant4 simulations, a benchmark test spectrometer was set up using a stack of four silicon detectors and a good agreement between the measured and simulated responses was found for a beta spectrum from a 90Sr/90Y source. The collimator design was optimized by adjusting total length, aperture size, number of view-ports and collimator materials. The optimum aperture size and the number of view-ports were determined by varying them and selecting the best cases that meet the angular resolution and the geometric factor requirements. Moreover, to address the under-utilization of the front position-sensitive detector encountered in a typical pin-hole collimator, two offset collimators with tilted axes were employed. Extensive simulations were carried out by varying the number of silicon detectors and the thickness of each detector to optimize the configuration of the silicon detector stack. An optimum thickness of the front detector was found to be 140 µm, which can minimize the perturbation counts caused by the proton detection events. For the other detectors, a stack of four 1.5 mm thick detectors was chosen to achieve a good sensitivity to low energy electrons at a tolerable complexity of the system. The angular response simulated for the optimum design of the EST showed a resolution of 5.5°, which is slightly better than the target resolution of 6°. The response matrices of the final design simulated for isotropic electron and proton fields showed a high geometric factor, which is expected to produce an average electron counting rate of 230 cps within the trapped region with a negligible contamination of the electron spectrum by protons except for a mild contamination by the 1.0–1.1 MeV protons.

Regulating the Layer Stacking Configuration of CTF-TiO2 Heterostructure for Improving the Photocatalytic CO2 Reduction.

Herein, covalent triazine frameworks in eclipsed AA and staggered AB stacking modes are respectively used for the in-situ growth of TiO2, and two heterostructures are obtained. Due to the highly organized stacking of the molecular layer in CTF-AA that strengthens the interlayer interaction, the light absorption and carrier migration of CTF-AA/TiO2 are both enhanced in comparison to those of its component or CTF-AB/TiO2. Correspondently, the photocatalytic CO2 reduction reaction (CO2RR) of CTF-AA/TiO2 proffers 9.19 μmol·g-1·h-1 CH4 and 2.32 μmol·g-1·h-1 CO production, about 9.2 and 4.3 times greater than that of pristine TiO2, respectively. Even though the innate photoresponse of the triazine unit endows CTF-AB/TiO2 with augmented light capturing, its photocatalytic CO2 conversion is relatively insignificant. According to the analyses of the planar-averaged electron density difference and Bader charge, the unproductive CO2 efficiency might be due to the insufficient interfacial electron transfer from TiO2 to CTF-AB. Given that the ΔG (-3.22 eV) of CHO intermediate generation is lower than that of CO desorption (-1.23 eV), the reaction tends to further generate CH4 other than yielding CO. This study could shed fresh light over the reasonable design of effective photocatalytic heterostructures.

Enhanced Transverse Dispersion in 3D-Printed Logpile Structures: A Comparative Analysis of Stacking Configurations

Three-dimensionally printed logpile structures have demonstrated the tunability of the transverse dispersion behavior, which is relevant in the context of chemical reactor design. The current modeling study aims to further investigate the trade-offs in such structures, extending the range of geometries investigated and addressing the limitations associated with the pseudo-2D nature of previous experiments. The relative transverse dispersion coefficient and pressure drop were determined using computational fluid dynamics simulations in OpenFOAM for structures with different stacking configurations, porosities and scaling of the structures’ unit cell along the secondary transverse axis. The latter could not be varied in previous experiments, but the current results demonstrate that this limitation suppresses vortex shedding in structures with high porosity. These vortices significantly enhance the transverse dispersion. By using a staggered stacking configuration on both transverse axes, an earlier onset of this phenomenon could be realized. Importantly, operation in this regime could be achieved without an equivalent increase in pressure drop, offering a favorable operating trade-off. The findings demonstrate that at low Reynolds numbers, the studied structures consistently outperform randomly packed beds of spheres, highlighting their potential for chemical process intensification.

Confined anionic electrons and their effect on physical properties of Ca2N bilayers with different stacking configurations

Ca2N is a unique two-dimensional material due to its confined anionic electrons. Unlike three-dimensional materials, the framework of Ca2N effectively confines the anionic electrons, leading to interesting physical and chemical properties. To study the electrical and optical properties of Ca2N bilayers with various stacking configurations, we used density functional theory calculations. This approach allowed us to investigate the behavior of anionic electrons located at the interlayer interface and at the surface. Using maximally localized Wannier functions to extract tight-binding parameters for each stacking configuration, we determined Hofstadter’s butterfly patterns for each structure, which provide a valuable insight into the influence of an external magnetic field on the electronic band structure. This work paves the way for further exploration of experimentally feasible configurations and their potential applications.

Vertical multilayer structure of MoS2 flakes prepared by thermal evaporative deposition

In this investigation, we explore the synthesis of MoS2 through thermal evaporative deposition, seeking to uncover the growth dynamics and structural evolution of MoS2 under varied experimental conditions. By adjusting the temperature and the carrier gas, this study targets the fabrication of vertical multilayer MoS2 and its growth mode. Our analysis demonstrates that thermal conditions markedly influence flake morphology and dimensions, leading to a notable shift from AA to AB stacking configurations as temperatures rise in the vacuum. Additionally, the application of carrier distinctly modifies growth behaviors, enhancing the uniformity of nucleation sites and the propensity for lateral flake expansion. The insights gained from this research highlight the adaptability and effectiveness of thermal evaporative deposition in producing MoS2, thereby enriching our understanding of the fundamental mechanisms guiding MoS2 synthesis.

Characterizing tensile and flexural properties of synthetic fibers-reinforced epoxy composite for foot prosthetic application

Materials have a direct and critical impact on the performance of prosthetic feet. This study investigates the mechanical properties of E-glass and hybrid (E-glass/carbon) epoxy composites for prosthetic foot applications. Using ANSYS FEA software, four stacking sequences were analyzed for tensile and flexural strength, with stacking configuration the SS-3 ([0c/90/45]s) demonstrating the highest performance. The numerical results were validated against analytical MATLAB solutions, showing excellent agreement. Compared to Homo-polymer-polypropylene, the composite prosthetic foot exhibits superior performance, with increased deformation resistance, energy storage capacity, safety factor, and stiffness, while reducing weight by 30.62 %. This study suggests a cost-effective and efficient method for developing lightweight and durable prosthetic feet that match the comfort and performance constraints of current HPP designs. The selected composite for prosthetic foot production was suggested due to its enhanced mechanical properties and improved functionality.

Effects of Acid Dissociation and Ionic Solutions on the Aggregation of 2-Pyrone-4,6-dicarboxylic Acid.

The conversion of lignin can produce biomass-derived aromatic compounds such as 2-pyrone-4,6-dicarboxylic acid (PDC), which is a potential sustainable precursor of bioplastics. PDC is a pseudoaromatic dicarboxylic acid that can aggregate in aqueous solution. Aggregation depends upon PDC-PDC, PDC-water, and PDC-ion interactions that are representative of interactions in similar charged, aromatic compounds. These interactions both dictate PDC aggregation and the likelihood that PDC aggregates exhibit parallel stacking configurations that may promote PDC crystallization, which can be leveraged to separate PDC from solution. However, the interplay of interactions that drive aggregation and structure formation, and how these depend upon the charge of PDC and ionic species present in solution, remains unclear. In this work, we investigate PDC aggregation in diverse ionic solutions using all-atom molecular dynamics simulations and molecular clustering analysis. We consider ion-induced dipole interactions by using a modified Lennard-Jones nonbonded model for divalent ions in solutions. From molecular clustering analysis, we derive characteristic parameters to quantify aggregate sizes and parallel stacking configurations. We show that acid dissociation facilitates PDC aggregation in ionic solutions via ion-mediated interactions, and different ionic solutions influence both the likelihood of aggregation and the formation of parallel aggregates. In particular, we find that parallel stacking is primarily found in solutions with monovalent ions, whereas divalent ions promote larger, but less structured, aggregates. These results provide molecular-scale insight into the effects of specific ions on the aggregation of like-charged PDC molecules to inform understanding of related separation processes.

Bilayer graphene, bilayer GeC and graphene/GeC bilayer heterostructure as anode materials for lithium-ion batteries: First-principles calculations

There is a great effort to develop the high-efficient anode materials for lithium-ion batteries with high stability and mobility. In this paper, we adopt the first-principles calculations to study the electrochemical properties of Li intercalation within bilayer graphene (BLG), bilayer GeC (BLGeC) and graphene/GeC bilayer heterostructure (BLGGeC) as anode materials. Our calculations disclose the following findings: (1) The interlayer is modulated by the stacking patterns and bilayer species. (2) The most energetically favorite intercalation of the Li atom is achieved in BLG with AA stacking because of the lowest adsorption energy. (3) The descending order of energy barriers is BLGGeC > BLGeC > BLG. The low diffusion barriers of BLG (0.025 eV) and BLGeC (0.09 eV) imply their high charging/discharging rates. Finally, the findings underline that the bilayer is a promising anode material and its electrochemical characteristics can be changed by adjusting the stacking configurations and its species.

Exploring the potential of metal tailored imine based covalent organic framework for asymmetric supercapacitor applications

Currently, a fascinating area of research involves the development of stable and efficient materials for energy storage systems. The current work describes the synthesis of imine linked covalent organic framework (COF) using 4,4′,4′',4′''-(ethene-1,1,2,2-tetrayl) tetraaniline and terephthalaldehyde (TAT-COF) as precursors through solvothermal method. In addition, cobalt has been integrated to the imine linkage of TAT-COF to generate CO@TAT-COF. The X-ray diffraction study reveals the formation of ordered and crystalline TAT-COF with eclipsed (AA) stacking configuration. Morphological characterization indicated the accumulation of metal species over stick like structured TAT-COF. Energy-dispersive X-ray (EDX) and Fourier Transform Infrared Spectroscopy results shows the successive intercalation of Co to the TAT-COF matrix. TAT-COF and Co@TAT-COF were examined towards electrochemical performance for supercapacitor applications. A two fold higher specific capacitance (Csp) was obtained in Co@TAT-COF (637 F/g) compared to TAT-COF (315 F/g) at 5 mV/s scan rate. The Co@TAT-COF showed an energy density (ED) of 58 Wh/kg at a power density of (PD) of 1500 W/kg. Enhanced electrochemical performance in Co@TAT-COF could be attributed to the structural confinement, conductivity, enhanced interlayer spacing and porosity. Co@TAT-COF has been used as positive electrode to fabricate an asymmetric device (ASD) in using Swagelok cell. The Csp of the fabricated ASD was found to be 95 F/g at 2 mV/s scan rate. ASD showed good stability with 73 % retention of Csp over 5000 charge/discharge cycles. The obtained results indicate the suitability of the engineered COFs towards energy storage devices.

Influence behavior and mechanism of double-layer Gr stacking configuration on mechanical strength and thermoelectric transport properties of Cu/Gr composites

The mechanical strength, electrical conductivity, and thermal conductivity of Cu/graphene (Gr) composites with Cu (111)/double-layer Gr/Cu (111) structure were investigated by using density functional theory and semi-classical Boltzmann transport theory. The results indicate that, the chemical bonds were generated between the two layers of Gr film, and the maximum charge densities of Gr-Top stacking configuration and Gr-Hollow stacking configuration are 0.104 and 0.118 e/Å3, respectively. Gr-Hollow stacking configuration has the larger mechanical strength and plasticity than Gr-Top stacking configuration. Although the covalent characteristic for the two stacking configurations is identical, the ionic characteristic of Gr-Top stacking configuration is stronger than Gr-Hollow stacking configuration. Therefore, the electron localization of Gr-Top stacking configuration is much stronger, leading to the smaller number of free electrons. The electrical conductivity and thermal conductivity of Gr-Hollow stacking configuration are 2.55 times and 1.63 times those of Gr-Top stacking configuration was achieved. Moreover, as the external longitudinal strain from 0 % to 15 % applied on Cu (111)/double-layer Gr/Cu (111) structure, the thermoelectric transport properties of Gr-Hollow stacking configuration are greater than Gr-Top stacking configuration, while as the strain are 20 % and 25 %, Gr-Top stacking configuration has the larger electric conductivity and thermal conductivity instead.

Influence of the electric field on the electronic structure of flat hexagonal two-dimensional GaN bilayers

Two-dimensional gallium nitride materials have recently garnered significant attention due to their promising optoelectronic properties, chemical stability, and mechanical strength. These attributes make them attractive for various technological applications, particularly optoelectronics, photonics, sensors, and more recently for high-power electronic applications. Our research, using first-principles calculations based on density functional theory (DFT) considering different exchange–correlation functionals, including van der Waals interaction, investigated the electronic properties of a single GaN monolayer and five different stacking configurations of GaN bilayers. The aim is to characterize the electronic properties of 2D-GaN-based materials and explore the impact of external electric fields on the bilayer stacking bandgap. We report the energetically most favorable among the bilayer configurations analyzed. Additionally, we confirmed that it is possible to modulate the energy bandgap both by the type of bilayer stacking and by the effect of the electric field. The ability to tune the energy bandgap (Eg) in 2D-GaN-based materials by adjusting their geometric configuration or applying an external electric field could inspire new applications in various technological fields.

Exploration toward a new stacking-pressure phase diagram in bilayer AA- and AB-MoS2

The phase diagram serves as a blueprint for designing the structure of a material, offering a comprehensive representation of its different phases under specific conditions, such as temperature and pressure. In the realm of two-dimensional (2D) materials, stacking order can play a crucial role in controlling and inducing phase transitions. However, in studying phase diagrams for 2D materials, the exploration of stacking degree of freedom has largely been overlooked, limiting our understanding and hindering future applications. Here, we experimentally explore the interplay of stacking and pressure degrees of freedom in revealing unique phase transitions in bilayer MoS2 with two different stacking configurations. In AA stacking, interlayer sliding and asymmetric intralayer compressing precede intralayer rotation, while in AB stacking, asymmetric intralayer compressing and intralayer distortion occur simultaneously. Under further elevated pressure, the bilayer system transitions into 1T′ phase before amorphization. Our findings offer valuable insights for creating comprehensive phase diagrams and exploring exotic phases as well as phase transitions of 2D materials in a broader parameter space.

Enhancing CO2 methanation via doping CeO2 to Ni/Al2O3 and stacking catalyst beds

This work synthesized a series of Ni/CeO2/Al2O3 catalysts with varying CeO2 doping amounts to enhance low-temperature CO2 methanation. The introduction of CeO2 weakens the interaction between Ni and Al2O3, leading to the formation of Ni-CeO2 active sites. This results in a high dispersion of Ni and CeO2, improved catalyst reducibility, increased number of active sites, and enhanced the CO2 methanation. This work further investigated the impact of WHSV and catalyst stacking configuration to enhance the reaction. When the catalyst is stacked into three segments with a temperature gradient of 330 °C, 300 °C, and 250 °C under WHSV = 9000 ml·h–1·(g cat)−1, the CO2 conversion significantly increases to 95%, which is remarkably close to the thermodynamic equilibrium (96%).

Probing the Effect of Alloying Elements on the Interfacial Segregation Behavior and Electronic Properties of Mg/Ti Interface via First-Principles Calculations.

The interface connects the reinforced phase and the matrix of materials, with its microstructure and interfacial configurations directly impacting the overall performance of composites. In this study, utilizing seven atomic layers of Mg(0001) and Ti(0001) surface slab models, four different Mg(0001)/Ti(0001) interfaces with varying atomic stacking configurations were constructed. The calculated interface adhesion energy and electronic bonding information of the Mg(0001)/Ti(0001) interface reveal that the HCP2 interface configuration exhibits the best stability. Moreover, Si, Ca, Sc, V, Cr, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, Sn, La, Ce, Nd, and Gd elements are introduced into the Mg/Ti interface layer or interfacial sublayer of the HCP2 configurations, and their interfacial segregation behavior is investigated systematically. The results indicate that Gd atom doping in the Mg(0001)/Ti(0001) interface exhibits the smallest heat of segregation, with a value of -5.83 eV. However, Ca and La atom doping in the Mg(0001)/Ti(0001) interface show larger heat of segregation, with values of 0.84 and 0.63 eV, respectively. This implies that the Gd atom exhibits a higher propensity to segregate at the interface, whereas the Ca and La atoms are less inclined to segregate. Moreover, the electronic density is thoroughly analyzed to elucidate the interfacial segregation behavior. The research findings presented in this paper offer valuable guidance and insights for designing the composition of magnesium-based composites.