Crystal State Research Articles

Crystalline phase-modulated PtOx nanoparticles exhibit superior methane combustion performance and sulfur poisoning resistance: Multi-interaction regulation

Up to now, methane combustion catalysts generally suffer from issues such as poor reaction stability and susceptibility to sulfur poisoning, which have become the key factors restricting their application, so it is necessary to construct catalysts with excellent chemical stability of the active center and strong sulfur resistance. Here, we showed the crystal phase-modulated state of PtOx nanoparticles (PtOx NPs) on TiO2 and investigated their effects on the reactivity of methane catalytic combustion and anti-SO2 poisoning properties. It was found that Pt/r-TiO2 showed superior activity, stability, and resistance to SO2 poisoning. Transmission electron microscope (TEM) images showed that the PtOx NPs on the surface of r-TiO2 were much more stable than a-TiO2 for the reason that the Ostwald ripening of PtOx NPs on a-TiO2 was facilitated due to the strong metal-support interaction (MSI) between PtOx NPs and TiO2 and the low migration energy of the PtOx NPs on TiO2, while they were moderate of Pt/r-TiO2, and then the active sites were stabilized during methane combustion. The activity was controlled by the size and electronic structure of PtOx NPs, which were stable on the surface of r-TiO2 with a higher Pt4+ content, and the density functional theory (DFT) calculations further revealed the role of r-TiO2 in increasing the quantities of surface oxygen vacancies. Moreover, the SO2 tolerance of Pt/r-TiO2 was also the best among all kinds of Pt-based catalysts prepared, which was attributed to the minimal adsorption energy (Ead) of SO2 on r-TiO2, and the absence of sulfate and sulfite deposition on the Pt/r-TiO2 catalyst confirmed by TGA and in-situ DRIFTS studies on SO2 adsorption. In this research, the anti-SO2 poisoning and reaction stability were realized by adjusting the interaction between SO2, active components, and supports, which provided a new insight for the design of stable Pt-based SO2-resistant catalysts.

Electronic states in one-dimensional helical crystals: General properties and application to InSeI

Electronic states in one-dimensional helical crystals: General properties and application to InSeI

Mo-doping modulated cationic vacancy in Zn3V2O8 with enhanced electrochemical performance for lithium-ion batteries

Given diverse redox reactions and abundant raw materials, Zn3V2O8 with high specific capacity is considered as a potential anode material for lithium-ion batteries. Same as other transition metal oxides, Zn3V2O8 suffers from infertile conductivity, sluggish ion diffusion and fast capacity loss derived from volume expansion during discharge/charge process, further hindering its application. In this work, a novel Mo doped Zn3V2O8 (Zn3V2-xMo5x/6O8) anode material with cationic vacancy (V vacancy) has been designed through a facile sol-gel method. It is found that a small Mo-doping amount has nearly no influence on the crystal structure, morphology and element valence states of Zn3V2O8. Mo doped Zn3V2O8 samples possess smaller charge transfer resistance and higher lithium ion diffusion coefficient. The results of electrochemical performance illustrate that Mo doped Zn3V2O8 can deliver higher reversible specific capacities and better rate capability compared with Zn3V2O8, which can be ascribed to the introduction of V vacancy. In particular, when Mo-doping amount is set as 0.03, the obtained Zn3V1.97Mo0.025O8 exhibits a reversible capacity of 481.1 mAh g−1 after 600 cycles at 1 A g−1. It is believed that this work could provide an effective and feasible strategy to construct high performance transition metal vanadate anode materials for lithium-ion batteries.

Theoretical Studies of Anisotropic Melting of Ice Induced by Ultrafast Nonthermal Heating.

Water and ice are routinely studied with X-rays to reveal their diverse structures and anomalous properties. We employ a hybrid collisional-radiative/molecular-dynamics method to explore how femtosecond X-ray pulses interact with hexagonal ice. We find that ice makes a phase transition into a crystalline plasma where its initial structure is maintained up to tens of femtoseconds. The ultrafast melting process occurs anisotropically, where different geometric configurations of the structure melt on different time scales. The transient state and anisotropic melting of crystals can be captured by X-ray diffraction, which impacts any study of crystalline structures probed by femtosecond X-ray lasers.

Advancements in The Cross-Linking and Morphology of Liquid Crystals

The liquid crystal state (LC) in polymer chemistry is a topic discussed in varied materials research. The anisotropic properties typical of these compounds are mostly the result of the presence of mesogens in the structure of liquid crystals. This article traces the development of liquid crystal science, focusing on liquid crystal epoxy resins (LCERs) and emphasizing the crucial role of mesogens and their diverse effect on the materials. It also highlights the importance of understanding the morphology of LC polymers, explaining their profound impact on material properties and performance. It explores the cross-linking process of liquid crystal resins and composites, describing how changes in structural factors affect material structure. The article also provides information about hardeners and their influence on the cross-linked structure. Various nanofillers were also discussed, elucidating their impact on the resulting composites.

O vacancy-rich doped WO3/GF as a novel electrode for an aqueous DHAQ/ K4Fe(CN)6 redox flow battery

In this study, a graphite felt (GF) electrode was modified with N and S heteroatoms before being loaded with Ti-doped or Nb-doped WO3 to produce Ti-WO3/GF-N-S and Nb-WO3/GF-N-S electrodes. X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy were used to analyze the crystal structure, morphology, and elemental state of the modified GF electrodes and investigate the impact of nonmetallic and metallic element doping. The influence of metal doping on the electronic distribution of the oxide was determined using first-principle calculations. The electrochemical properties of the modified GF were studied using cyclic voltammetry, electrochemical impedance spectroscopy, and single-cell tests. The results showed that Ti or Nb doping changed the energy band structure, bond length, and bond angle in the WO3 crystal and formed O vacancies. The chemical properties of Ti and Nb resulted in different numbers of O vacancies for the two doped-WO3.The doping of N and S heteroatoms on the carbon fibres altered the O vacancy concentration of WO3. The synergism between the two doping methods accelerated electron transfer in the anthraquinone redox reaction. In addition, the N-containing functional groups provide lone-pair electrons, which accelerate electron transfer and anthraquinone adsorption. Therefore, compared to the pristine GF, the discharge capacities of the Ti-WO3/GF-N-S and Nb-h-WO3/GF-N-S graphite GF electrodes increased by 58 % and 41 %, respectively, and the Nb-h-WO3/GF-N-S graphite GF electrodes exhibited a good capacity retention rate. This study broadens the practical applications of aqueous anthraquinone redox flow batteries.

Effect of Hydrogen Bonding and Chirality in Star-Shaped Molecules with Peripheral Triphenylamines: Liquid Crystal Semiconductors and Gels.

Organic semiconductors with well-defined architectures pose a suitable alternative to amorphous silicon-based inorganic semiconductors. Encouraged by the development of organic semiconductors based on columnar liquid crystals, herein, we report on a family of C3-symmetric star-shaped mesogens based on triphenylamine (TPA), a functional unit with strong electron donor character. Highly stable columnar phases with high hole mobility values were obtained out of this nonplanar functional unit, and this was achieved by using flexible amide spacers to join the TPA units to a tris(triazolyl)triazine (T) star-shaped core, allowing the formation of intermolecular hydrogen bonds. The presence of hydrogen bonds results in a stabilization of the columnar architectures either in bulk or in the presence of solvents by reinforcing π-stacking and van der Waals interactions, as deduced by Fourier-transform infrared (FTIR) and X-ray diffraction (XRD) studies. Furthermore, the introduction of a stereogenic center in the flexible spacer prompts the formation of chiral aggregates in the liquid crystal state and in the organogel formed in 1-octanol, as demonstrated by circular dichroism spectroscopy.

Impact of nanoconfinement on the physical state and conductivity mechanisms of a 2-picolinium ionic liquid crystal

Hybrid solid-like materials prepared from the incorporation of liquid-like ionic conductors into nanoporous matrices could represent an advantage for a variety of electronic applications. Aiming to obtain such materials, three composites of the polymorphic ionic liquid crystal (ILC) 1-hexadecyl-2-methylpyridinium bromide ([C16-2-Pic][Br]), loaded in the mesoporous inorganic silica SBA-15 (∼6.8 nm in pore diameter), were prepared at guest–host weight fractions of ∼ 40, 60 and 80% (w/w) and investigated by different techniques: ATR-FTIR, BET, TGA, XRD and DSC. Complete amorphisation was achieved for the 40 and 60% composites, while the 80% preparation was stabilised in the low-T morph of native C16, being in the liquid state at room temperature. Furthermore, through Dielectric Relaxation Spectroscopy, the ionic conductivity of the three hybrid materials was characterised, allowing to deconvolute this property in a pure ohmic contribution (conductivity I) and the overlapping of ac − dc transition with interfacial polarisation resulting from the coexistence of the ionic liquid and the quasi-insulating inorganic matrix (conductivity II). From –20 to 20 °C, the conductivity and the corresponding charge migration are faster in all composites relative to the neat ILC, as deduced from the inferior radii of Nyquist arcs. The 60% preparation stood out from the other materials, exhibiting direct conductivity unaffected by electrode polarisation over a larger T-range, leading to the assumption of a nearly continuous silica-mediated charge migration pathway, which is never reached for the 40% composite, while, in the 80% preparation, some C16 deposits on the outer surface of the pores. Incorporation into the silica matrix proved to be a good strategy for the production of cost-efficient materials with long-term stabilisation of the ionic liquid in a single phase over a large range of temperatures, enabling the prediction of flow and conductive properties.

Dualistic insulator states in 1T-TaS2 crystals

While the monolayer sheet is well-established as a Mott-insulator with a finite energy gap, the insulating nature of bulk 1T-TaS2 crystals remains ambiguous due to their varying dimensionalities and alterable interlayer coupling. In this study, we present a unique approach to unlock the intertwined two-dimensional Mott-insulator and three-dimensional band-insulator states in bulk 1T-TaS2 crystals by structuring a laddering stack along the out-of-plane direction. Through modulating the interlayer coupling, the insulating nature can be switched between band-insulator and Mott-insulator mechanisms. Our findings demonstrate the duality of insulating nature in 1T-TaS2 crystals. By manipulating the translational degree of freedom in layered crystals, our discovery presents a promising strategy for exploring fascinating physics, independent of their dimensionality, thereby offering a “three-dimensional” control for the era of slidetronics.

Observation of Landau levels and chiral edge states in photonic crystals through pseudomagnetic fields induced by synthetic strain

Observation of Landau levels and chiral edge states in photonic crystals through pseudomagnetic fields induced by synthetic strain

Electrosynthesis of nitrate by FeS2-TiO2 heterogeneous nanoparticles supported on 2-methylimidazolium functionalized polypyrrole/graphene oxide

Electrochemical nitrogen oxidation reaction (NOR) acts as a clean and sustainable approach for promisingly replacing the conventional industrial method for producing nitrate. Designing and preparing the effective electrocatalysts for NOR has aroused great research interests. Herein, FeS2-TiO2 heterostructures are well-dispersed on the surface of 2-methylimidazolium functionalized polypyrrole/graphene oxide (2-MeIm/PPy/GO) by the in situ growth due to the ion-exchange and the coordination between the 2-MeIm groups and the metal precursors, which exhibit the excellent NOR electroactivity. The highest NO3– yield by the obtained FeS2-TiO2@2-MeIm/PPy/GO reaches to 137.04 μg h−1 mg-1act. with the maximum Faradic efficiency (FE) of 4.38 % at 2.04 V (vs. RHE), better than most reported electrocatalysts. The good selectivity for producing nitrate is also achieved, but the stability of both the NO3– yield and FE present a trend of rising and then declining in the cyclic test of FeS2-TiO2@2-MeIm/PPy/GO. The irreversible conversion of the electrocatalysts can be confirmed through detailed characterization towards the crystal structures and chemical states of FeS2-TiO2@2-MeIm/PPy/GO after long term NOR test. The electrochemical step of NOR mainly occurs at FeS2, converting the inert N2 to active *NO intermediates. SO42- generated at high NOR potential gradually increase by the oxidation of S element, which can cause the promotion of the NOR performance before the fourth cycle. But along with the disappearance of FeS2 phase, FeS2-TiO2 as the catalytic center is finally irreversibly converted to Fe and S ions doped TiO2, resulting in the sharp drop of both the NO3– yield and FE at the sixth cycle. This work will provide valuable guidance for the designing and preparing NOR electrocatalysts.

Topological protection of dual-polarization biphoton states in photonic crystals

Polarization control is a major issue in topological quantum optics that limits reliable generation and transmission of quantum states. This study presents what we believe to be a novel topological photonic crystal design that provides topological protection for biphoton pairs for both TE and TM polarization. By well-designed cell configurations within the lattice, two topological boundaries emerge that can accommodate TM and TE modes at the same time. By adjusting the dispersion curves, we can further design nonlinear four-wave mixing processes within the topological photonic crystals and provide theoretical explanations for the entanglement of the dual-polarization biphoton states. Numerical results confirm the robust transport of entangled photon pairs, even when subjected to sharp bending. Moreover, combining the dual-polarization topological photonic crystal with a polarization beam splitter enables the preparation of polarization-encoded maximally entangled states. Our work exhibits significant potential for applications in robust optical quantum information processing and quantum secure communication.

Engineering Clock Transitions in Molecular Lanthanide Complexes.

Molecular lanthanide (Ln) complexes are promising candidates for the development of next-generation quantum technologies. High-symmetry structures incorporating integer spin Ln ions can give rise to well-isolated crystal field quasi-doublet ground states, i.e., quantum two-level systems that may serve as the basis for magnetic qubits. Recent work has shown that symmetry lowering of the coordination environment around the Ln ion can produce an avoided crossing or clock transition within the ground doublet, leading to significantly enhanced coherence. Here, we employ single-crystal high-frequency electron paramagnetic resonance spectroscopy and high-level ab initio calculations to carry out a detailed investigation of the nine-coordinate complexes, [HoIIIL1L2], where L1 = 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraaza-cyclododecane and L2 = F- (1) or [MeCN]0 (2). The pseudo-4-fold symmetry imposed by the neutral organic ligand scaffold (L1) and the apical anionic fluoride ion generates a strong axial anisotropy with an mJ = ±8 ground-state quasi-doublet in 1, where mJ denotes the projection of the J = 8 spin-orbital moment onto the ∼C4 axis. Meanwhile, off-diagonal crystal field interactions give rise to a giant 116.4 ± 1.0 GHz clock transition within this doublet. We then demonstrate targeted crystal field engineering of the clock transition by replacing F- with neutral MeCN (2), resulting in an increase in the clock transition frequency by a factor of 2.2. The experimental results are in broad agreement with quantum chemical calculations. This tunability is highly desirable because decoherence caused by second-order sensitivity to magnetic noise scales inversely with the clock transition frequency.

Thermally Stimulated Transformation of Oxygen Atoms Between Phase States in a Silicon Single Crystal

Thermally Stimulated Transformation of Oxygen Atoms Between Phase States in a Silicon Single Crystal

From a vortex gas to a vortex crystal in instability-driven two-dimensional turbulence

We study structure formation in two-dimensional turbulence driven by an external force, interpolating between linear instability forcing and random stirring, subject to nonlinear damping. Using extensive direct numerical simulations, we uncover a rich parameter space featuring four distinct branches of stationary solutions: large-scale vortices, hybrid states with embedded shielded vortices (SVs) of either sign, and two states composed of many similar SVs. Of the latter, the first is a dense vortex gas where all SVs have the same sign and diffuse across the domain. The second is a hexagonal vortex crystal forming from this gas when the linear instability is sufficiently weak. These solutions coexist stably over a wide parameter range. The late-time evolution of the system from small-amplitude initial conditions is nearly self-similar, involving three phases: initial inverse cascade, random nucleation of SVs from turbulence and, once a critical number of vortices is reached, a phase of explosive nucleation of SVs, leading to a statistically stationary state. The vortex gas is continued in the forcing parameter, revealing a sharp transition towards the crystal state as the forcing strength decreases. This transition is analysed in terms of the diffusivity of individual vortices using ideas from statistical physics. The crystal can also decay via an inverse cascade resulting from the breakdown of shielding or insufficient nonlinear damping acting on SVs. Our study highlights the importance of the forcing details in two-dimensional turbulence and reveals the presence of non-trivial SV states in this system, specifically the emergence and melting of a vortex crystal.

Johnson–Cook yield functions for cyclotetramethylene-tetranitramine (HMX) and cyclotrimethylene-trinitramine (RDX) derived from single crystal plasticity models

High-fidelity constitutive models are critical for accurate meso-scale continuum modeling and prediction of shock initiation of crystalline energetic materials (EMs). While empirically calibrated or atomistic-guided anisotropic elastoplastic models of EM such as cyclotetramethylene-tetranitramine (HMX) and cyclotrimethylene-trinitramine (RDX) capture important micromechanical phenomena (such as dislocation evolution, slip-resistance, and anisotropic elasticity), the computational cost of using anisotropic single-crystal plasticity models can become prohibitive for meso-scale computations of void-collapse and hotspot formation in microstructures. Thermo-mechanically representative, isotropic, pressure, temperature, and rate-dependent material constitutive models are practical alternatives for meso-scale simulations of the shock response of microstructures. To this end, this work constructs physically consistent isotropic plasticity from anisotropic single-crystal plasticity models for HMX and RDX. State-of-the-art crystal plasticity models for HMX and RDX are used to compute the stress states in single crystals oriented in three different directions relative to shocks generated by impact at velocities ranging from 100 to 1000 m/s. Post-shock von Mises stress fields for the three orientations are then used to calibrate the strain-rate hardening coefficient and the reference strain rate for a rate-dependent Johnson–Cook (JC) yield surface model. We compare the pressures and the post-shock von Mises stresses between the JC and the anisotropic models to show that the isotropic computations closely approximate the averaged deformation response of the three different crystal orientations. We then model the interaction of a shock generated by a 500 m/s impact with a 0.5 μm void and show that the pressures and the deviatoric stresses obtained using the isotropic model closely match those computed from anisotropic models for both HMX and RDX. The resulting isotropic J2 plastic flow model for HMX and RDX can be employed to perform meso-scale simulations for energy localization due to shear bands and void collapse in the two materials.

Two viologen-based complexes as persistent luminescent materials and their applications in inkless print and anticounterfeiting

Viologen-based complexes have garnered significant attention due to their multifunctional stimuli-responsive properties and tunable persistent luminescence. However, achieving ultralong afterglow emission and color change in these complexes remains a challenge, limiting their application in the field of persistent luminescence. Herein, two novel viologen-based complexes were successfully designed and synthesized using N,N′-bis(2-carboxyethyl)-4,4′-bipyridinium dichloride (H2bybpy) ligands and trimesic acid (H3BTC) with the transition metals Zn(II)/Cd(II). Complexes 1 and 2 display reversible photochromic and electrochromic properties. Interestingly, complexes 1 and 2 in their crystal state exhibit dual fluorescence and persistent luminescence, emitting a green and cyan afterglow when the UV lamp is turned off at 77 K. Incorporating phosphorescent molecules and changing the metal significantly extended the duration of persistent luminescence and altered the hue. The complexes were also demonstrated to have potential applications in inkless printing, color-changing films, data encryption, and anti-counterfeiting. This work enhances the application of viologen-based complexes in light-controlled persistent fluorescence and provides ideas for achieving ultra-long afterglow emission.

Electronic properties of the barium magnesium tantalate

BaMg1/3Ta2/3O3 (BMT) crystals belong to the family of complex perovskites and are well known for their excellent microwave dielectric properties. In this work, structural optimization of the lattice parameters was performed. Electron density functional theory calculations of the electronic band structure of BMT crystal of the trigonal phase were carried out along Г–A–K–M–L directions of the Brillouin zone. The calculated band gap energy was 3.554 eV. The partial density of states of BMT crystal in P-3 m1 phase was simulated. Top of the valence band was formed by 2p-states of O and bottom of the conduction band – by 5d-states of Ta.

Investigation of magnetotransport properties of topological surface states in SnBi4Te7 single crystal

Investigation of magnetotransport properties of topological surface states in SnBi4Te7 single crystal

Raman spectroscopic evaluation of structural-phase state of titanium and zirconium pseudo-single crystals deformed in Bridgman anvils

A complex study of the microstructure of titanium and zirconium pseudo-single crystals subjected to severe plastic deformation in Bridgman anvils under a pressure of 8 GPa at a temperature of 80 K has been carried out. Raman spectra of the samples deformed to different degrees show a two-phase α + ω state, which indicates the realization of the pressure-induced transition during deformation process with the retention of the ω-phase in the structure of both metals after the load removal. The quantitative ratio of α- and ω- phases in the structure of deformed metals and its change with increasing degree of deformation has been analyzed.Correlation of Raman spectroscopy results with experimental data of X-ray diffraction analysis, electron microscopic analysis, as well as literature data of calorimetry and calculated thermodynamic data by DFT method on kinetics of the reverse ω → α transformation demonstrates the efficiency of Raman spectroscopy method for estimation of the phase composition of pure metals, which experienced phase transition under loading.