Bulk Phase Transition Research Articles

Stabilizing 4.6 V LiCoO2 via Surface‐to‐Bulk Titanium Modification

AbstractElevating the charging cut‐off voltage is an effective strategy to increase the energy density of LiCoO2. However, unstable interfacial structures and unfavorable phase transitions in bulk are inevitably triggered during deep de‐lithiation at high voltage. Herein, an integrated surface‐to‐bulk Ti‐modification strategy is applied to LiCoO2, enabling uniform Li2TiO3 coating on the surface and gradient Ti‐doping toward the structural bulk. The resultant Ti‐modified LiCoO2 (T‐LCO) electrode can be stably cycled up to 4.6 V, providing a high‐rate capability of 137 mAh g−1 at 5C and a long‐life stability with 80.5% capacity retention after 400 cycles at 1C, far outperforming the unmodified LiCoO2 electrode with only 50.7% capacity retention. In situ X‐ray diffraction characterization and density functional theory calculation reveal that the synergistic modification of T‐LCO enhances Li+ diffusion, facilitates the construction of high‐quality cathode/electrolyte interphase, reduces the phase transition from O3 to H1‐3 and Co3d/O2p band overlap, and restrains layer‐to‐spinel phase distortion, thus improving structural stability at 4.6 V. This work presents a “two birds one step” strategy to enhance the cycling stability and achievable capacity of high‐voltage LiCoO2 for developing high energy density lithium‐ion batteries.

Microscopic Thermo‐Mechanical Properties and Phase Transition of Bulk Ice‐Ih

Microscopic Thermo‐Mechanical Properties and Phase Transition of Bulk Ice‐Ih

Extraordinary phase transition revealed in a van der Waals antiferromagnet

While the surface-bulk correspondence has been ubiquitously shown in topological phases, the relationship between surface and bulk in Landau-like phases is much less explored. Theoretical investigations since 1970s for semi-infinite systems have predicted the possibility of the surface order emerging at a higher temperature than the bulk, clearly illustrating a counterintuitive situation and greatly enriching phase transitions. But experimental realizations of this prediction remain missing. Here, we demonstrate the higher-temperature surface and lower-temperature bulk phase transitions in CrSBr, a van der Waals (vdW) layered antiferromagnet. We leverage the surface sensitivity of electric dipole second harmonic generation (SHG) to resolve surface magnetism, the bulk nature of electric quadrupole SHG to probe bulk spin correlations, and their interference to capture the two magnetic domain states. Our density functional theory calculations show the suppression of ferromagnetic-antiferromagnetic competition at the surface is responsible for this enhanced surface magnetism. Our results not only show counterintuitive, richer phase transitions in vdW magnets, but also provide viable ways to enhance magnetism in their 2D form.

Infrared fixed point in the massless twelve-flavor SU(3) gauge-fermion system

We present strong numerical evidence for the existence of an infrared fixed point in the renormalization group flow of the SU(3) gauge-fermion system with twelve massless fermions in the fundamental representation. Our numerical simulations using nHYP-smeared staggered fermions with Pauli-Villars improvement do not exhibit any first-order bulk phase transition in the investigated parameter region. We utilize an infinite volume renormalization scheme based on the gradient flow transformation to determine the renormalization group β function. The gradient flow β function exhibits a zero at gGF⋆2=6.60(62), implying that the system is infrared conformal. We calculate the leading irrelevant critical exponent γg⋆=0.199(32). Our prediction for γg⋆ is consistent with available literature at the 1−2σ level. Published by the American Physical Society 2024

Colossal c-Axis Response and Lack of Rotational Symmetry Breaking within the Kagome Planes of the CsV_{3}Sb_{5} Superconductor.

The kagome materials AV_{3}Sb_{5} (A=K, Rb, Cs) host an intriguing interplay between unconventional superconductivity and charge-density waves. Here, we investigate CsV_{3}Sb_{5} by combining high-resolution thermal-expansion, heat-capacity, and electrical resistance under strain measurements. We directly unveil that the superconducting and charge-ordered states strongly compete, and that this competition is dramatically influenced by tuning the crystallographic c axis. In addition, we report the absence of additional bulk phase transitions within the charge-ordered state, notably associated with rotational symmetry breaking within the kagome planes. This suggests that any breaking of the C_{6} invariance occurs via different stacking of C_{6}-symmetric kagome patterns. Finally, we find that the charge-density-wave phase exhibits an enhanced A_{1g}-symmetric elastoresistance coefficient, whose large increase at low temperature is driven by electronic degrees of freedom.

Electrostatic shielding effects and binding energy shifts and topological phases of bilayer molybdenum chalcogenides

AbstractBy combining binding energy and bond‐charge (BBC) model and density functional theory (DFT) calculations, the electrostatic shielding effects and binding energy shifts of bilayer MoS2, MoSe2, and MoTe2 are studied. In this study, the bilayer MoS2, MoSe2, and MoTe2 had bandgaps of 1.38, 1.28, and 1.01 eV, respectively. It is found that electrostatic shielding by electron exchange is the main cause of density fluctuation and determine the bonding state. We found that the edge polarization exactly vanishes after the bulk phase transition, just as we saw the corner‐localized modes disappear in a system with full open boundaries of bilayer MoTe2. Finally, this study establishes a method for calculating the lattice density with Green's function with energy level shift and provides new methods and ideas for the further study of the electrostatic shielding, bond states and topological phases of nanomaterials.

Exploiting phase transitions in catalysis: reaction of and on doped -polymorphs

is well known for its reversible transition between two phases with tetragonal rutile and monoclinic structure. In a previous theoretical study (Stahl and Bredow 2022 ChemPhysChem 23 e202200131) we showed that the adsorption energy of CO is different on surfaces of the two Mo-stabilized polymorphs. This can be exploited to promote catalytic reactions by removing CO from the catalyst surface. As proof-of-principle, we investigated the hydrogenation reaction of . For this purpose, the adsorption energies of and possible intermediates and products , HCOOH, and CO were calculated. Significant differences were found for the reaction energies of the hydrogenation of to formic acid and formaldehyde on the two polymorphs. This shows that it is in principle possible to alter the reaction thermodynamics by applying reaction conditions which stabilize a particular polymorph. In order to investigate the influence of the polymorph on kinetic properties, the reactions barriers of a step-wise reaction of was calculated using the nudged elastic band method. was found to reduce the reaction barriers compared to the gas phase. Additionally, the minimum energy path of the bulk phase transition of undoped was calculated using the distinguished reaction coordinate method. A catalytic cycle exploiting the phase transition is proposed based on the theoretical results.

Consistent interpretation of isotope and chemical oxygen exchange relaxation kinetics in SrFe0.85Mo0.15O3-δ ferrite.

This paper is devoted to the study of phase composition and kinetic and thermodynamic characteristics of Mo-doped strontium ferrite SrFe0.85Mo0.15O3-δ (SFM15) under oxygen-conducting membrane working conditions. Single-phase SFM15 with a cubic Pm3̄m structure was synthesized using a ceramic method. It was shown that the molybdenum introduction stabilizes the perovskite cubic structure over a wide range of oxygen pressures and temperatures, preventing the bulk phase transition at high temperatures. Oxygen exchange constants, diffusion coefficients and activation energy of oxygen exchange were obtained using oxygen relaxation and isotopic exchange techniques, and the obtained values are consistent with known literature data. It was shown that the surface reaction rates obtained using chemical and tracer relaxation methods are quantitatively comparable with each other, despite significantly different experimental conditions. This result not only confirms the reliability of the data obtained by independent methods, but also allows one to expand the area of physical conditions for studying the kinetics of oxygen transfer where another method has technical or methodological limitations.

EFFECT OF h-BN AS AN ADDITIVE ON PHYSICAL AND MECHANICAL PROPERTIES OF Al2TiO5 COMPOSITE

Aluminum titanate (Al2TiO5) is a promising material for high-temperature applications due to its low thermal expansion, high melting point, and excellent corrosion resistance. In this study, the effect of h-BN addition on the properties of Al2TiO5 composites was investigated. The composites were prepared by sintering a mixture of Al2O3 and TiO2 at a 1:1 molar ratio, with varying amounts of h-BN (5-20 mol%) added to the mixture. The samples were sintered at 1,500ºC for 4 h in an N2 atmosphere, and the bulk density, porosity, phase transition, microstructure, flexural strength, and hardness of the composites were investigated. XRD analysis confirmed the presence of Al2TiO5, Al2O3, and Al18B4O33 phases in the composites. The addition of h-BN in increasing amounts from 5 to 20 mol% resulted in a gradual improvement in the bulk density, flexural strength, and hardness of the Al2TiO5 composites. The composite with the highest h-BN content (20 mol%) exhibited a bulk density of 3.12 g/cm3, as well as the highest flexural strength and hardness values of 123.6±8.9 MPa and 11.2±4.1 GPa, respectively.

Symmetry indicators in commensurate magnetic flux

We derive a framework to apply topological quantum chemistry in systems subject to magnetic flux. We start by deriving the action of spatial symmetry operators in a uniform magnetic field, which extends Zak's magnetic translation groups to all crystal symmetry groups. Ultimately, the magnetic symmetries form a projective representation of the crystal symmetry group. As a consequence, band representations acquire an extra gauge invariant phase compared to the non-magnetic theory. Thus, the theory of symmetry indicators is distinct from the non-magnetic case. We give examples of new symmetry indicators that appear at $\pi$ flux. Finally, we apply our results to an obstructed atomic insulator with corner states in a magnetic field. The symmetry indicators reveal a topological-to-trivial phase transition at finite flux, which is confirmed by a Hofstadter butterfly calculation. The bulk phase transition provides a new probe of higher order topology in certain obstructed atomic insulators.

Phase Transition of Zeolite X under High Pressure and Temperature

AbstractX-ray powder diffraction study was conducted on the bulk modulus and phase transition behavior of synthetic zeolite X under high temperature and high pressure. Water and HCO3- solution were used as a PTM. Sample was heated and pressurized up to 250 °C and 5.18 GPa. The change of unit cell volume and phase transition were observed by X-ray diffraction. The lattice constants and unit cell volume of zeolite X, gmelinite, natrolite, and smectite were calculated using the GSAS2 program to which Le Bail’s whole powder pattern decomposition (WPPD) method was applied. The bulk modulus of each zeolite X and smectite were calculated using the EosFit program to which the Birch-Murnaghan equation was applied. The bulk modulus of zeolite X is 89(3) GPa in water run, and zeolite X is 92(3) GPa in HCO3- solution run. In both run, pressure induced hydration (PIH) occurred due to the inflow of PTM into the zeolite X framework at initial pressure. Zeolite X transited to gmelinite, natrolite, and smectite in water run. Zeolite X, however, transited to smectite in HCO3- solution run. Interzeolite transformation occurred in water run, and did not occur in HCO3- solution run, which is assumed that conflict between the environment to form zeolite and the pH of the HCO3- solution.합성 제올라이트 X의 고온 고압 하에서 압력 전달 매개체에 따른 체적탄성계수와 상전이 특성을 이해하기 위해 X-선 분말 회절 연구를 진행하였다. 제올라이트 X에 물과 탄산 용액을 압력전달매개체로 사용하여 상온 상압에서 최대 250 ℃, 5.18 GPa까지 가열 및 가압하는 과정에서 나타나는 단위포 부피 변화와 상전이를 방사광 X-선 회절을 통해 관찰하였다. 르바일의 전체 분말 패턴 분해법이 적용된 GSAS2 프로그램을 사용하여 각 압력 단계에서 제올라이트 X와 그멜리나이트, 나트로라이트, 스멕타이트의 격자상수와 단위포 부피를 도출하였다. 버치-머내한 2차 방정식이 적용된 EosFIt 프로그램을 사용하여 각 제올라이트 X와 스멕타이트의 체적탄성계수를 구하였다. 물을 사용한 실험에서 제올라이트 X의 체적탄성계수는 89(3) GPa, 탄산 수용액을 사용한 실험에서 제올라이트 X의 체적탄성계수는 92(3) GPa이다. 두 실험 모두 최초 가압 시 제올라이트 X 내부로 압력 전달매개체의 유입으로 인한 부피 증가 현상이 발생하였다. 물을 사용한 실험에서 제올라이트 X는 그멜리나이트, 나트로라이트, 스멕타이트로 상전이 하였으며, 탄산 수용액을 사용한 실험에서 제올라이트 X는 스멕타이트로 상전이 하였다. 물을 사용한 실험에서 나타난 제올라이트 간 변화는 탄산 수용액을 사용한 실험에서는 발생하지 않았으며, 이는 특정 제올라이트 생성 조건이 압력 전달 매개체 pH와 연관이 있는 것으로 판단된다.Keywords : Zeolite X, phase transition, bulk modulus, temperature, pressure

Kinetic Analysis of the Cation Exchange in Nanorods from Cu2-xS to CuInS2: Influence of Djurleite's Phase Transition Temperature on the Mechanism.

In the syntheses of ternary I-III-VI2 compounds, such as CuInS2, it is often difficult to balance three precursor reactivities to achieve the desired size, shape, and atomic composition of nanocrystals. Cation exchange reactions offer an attractive two-step alternative, by producing a binary compound with the desired morphology and incorporating another atomic species postsynthetically. However, the kinetics of such cation exchange reactions, especially for anisotropic nanocrystals, are still not fully understood. Here, we present the cation exchange reaction from Cu-deficient djurleite Cu2-xS nanorods to wurtzite CuInS2, with size and shape retention. With reaction parameters in a broad temperature range between 40 °C and 160 °C, we were able to obtain various intermediates. Djurleite has a bulk phase transition temperature at 93 °C, which influences the cation exchange considerably. Below the phase transition temperature, indium is only incorporated into the surface of the nanorods, while, at temperatures above the phase transition temperature, we observe a Janus-type exchange mechanism and the formation of CuInS2 bands in the djurleite nanorods. The findings suggest that the diffusion above the phase transition temperature is strongly favored along the copper planes of the copper sulfide nanorods over the diffusion through the sulfur planes. This results in a difference of 37 kJ mol-1 in the activation energy of the cation exchange below and above the phase transition temperature.

In situ diffraction monitoring of nanocrystals structure evolving during catalytic reaction at their surface

With decreasing size of crystals the number of their surface atoms becomes comparable to the number of bulk atoms and their powder diffraction pattern becomes sensitive to a changing surface structure. On the example of nanocrystalline gold supported on also nanocrystalline {text{CeO}}_2 we show evolution of (a) the background pattern due to chemisorption phenomena, (b) peak positions due to adsorption on nonstoichiometric {text{CeO}}_{2-x} particles, (c) Au peaks intensity. The results of the measurements, complemented with mass spectrometry gas analysis, point to (1) a multiply twinned structure of gold, (2) high mobility of Au atoms enabling transport phenomena of Au atoms to the surface of ceria while varying the amount of Au in the crystalline form, and (3) reversible {text{CeO}}_2 peaks position shifts on exposure to He–X–He where X is O2, H2, CO or CO oxidation reaction mixture, suggesting solely internal alternations of the {text{CeO}}_2 crystal structure. We found no evidence of ceria lattice oxygen being consumed/supplied at any stage of the process. The work shows possibility of structurally interpreting different contributions to the multi-phase powder diffraction pattern during a complex physico-chemical process, including effects of physi-, chemisorption and surface evolution. It shows a way to structurally interpret heterogeneous catalytic reactions even if no bulk phase transition is involved.

Catalytic Activity of BaTiO3 Nanoparticles for Wastewater Treatment: Piezo- or Sono-Driven?

Piezocatalytic reactions are generally excited by ultrasonication and, as such, should occur simultaneously with other catalytic reactions caused by different mechanisms such as sonocatalysis or tribocatalysis. One of the main challenges is how to discriminate between these effects in a catalysis experiment and quantify each contribution. In order to distinguish these effects, we use nano- and micro-particles of piezoelectric barium titanate (BaTiO3) and then compare their catalytic properties below and close to the piezoelectric to non-piezoelectric phase transition temperature at which the crystalline structure changes from the low-temperature tetragonal, piezoelectric phase to the higher-temperature cubic, non-piezoelectric phase. All other parameters, such as particle size, surface termination, etc., remain unaltered. The phase transition in bulk occurs at about 120 °C, but the transition temperature decreases as a function of particle size and reaches room temperature for particle sizes of about 20 nm. Transmission electron microscopy and X-ray diffraction were used to characterize the morphology and crystalline phase of the nanoparticles, respectively. Since the piezoelectric properties and the lattice dynamics are closely related, temperature-dependent Raman spectroscopy provides an even better insight into the nano- and micro-structural properties, allowing the ferroelectric phase transition temperature to be estimated. The catalytic activities of the BaTiO3 nanoparticles were determined by monitoring the optical absorption of a solution containing the model pollutant methyl orange, after ultrasonication of the solution to which were added the dispersed piezoelectric BaTiO3 particles as catalysts. An exponential-like correlation has been found between the catalytic reaction rates and the tetragonal distortion of the crystal structure of the BaTiO3 particles. Our study has also established that while 10% of the catalytic reaction of BaTiO3 is related to either sonocatalysis or tribocatalysis, the remaining 90% of the overall catalytic activity is ascribed to the piezocatalytic contribution.

Influence of the Molecular Structure on the Electrocatalytic Hydrogenation of Carbonyl Groups and H2 Evolution on Pd

We investigated the electrocatalytic hydrogenation (ECH) of model aldehydes and ketones over carbon-supported Pd in the aqueous phase. We propose reaction mechanisms based on kinetic measurements and on spectroscopic and electrochemical characterization of the working catalyst. The reaction rates of ECH and of the H2 evolution reaction (HER) vary with the applied electric potential following trends that strongly depend on the organic substrate. The intrinsic rates of hydrogenation and H2 evolution are influenced, in opposing ways, by the sorption of the reacting organic substrate. Strong interactions, that is, higher standard free energies of adsorption of the organic compound, induce high hydrogenation rates. The fast hydrogenation kinetics produces a hydrogen-depleted environment that kinetically hinders the HER and the bulk phase transition of Pd to a H-rich bulk Pd hydride, which is triggered by the applied potential in the absence of reacting organic compounds. As a consequence of strong organic–metal interactions, hydrogenation dominates at low overpotential. However, the coverages of organic substrates on the metal surface decrease, and the rates of H2 evolution surpass those of hydrogenation with increasingly negative electric potential. We determined the range of electric potential favoring hydrogenation on Pd and quantitatively deconvoluted the effects of the sorption of the organic compound, and of the rates of proton-coupled electron transfers, on the kinetics of both ECH and HER. The results indicate that electrocatalysis offers hydrogenation pathways for polar molecules which are different and, in some cases, faster than those dominating in the absence of an external electric potential.

Lattice studies of the Sp(4) gauge theory with two fundamental and three antisymmetric Dirac fermions

We consider the $Sp(4)$ gauge theory coupled to $N_f=2$ fundamental and $n_f=3$ antisymmetric flavours of Dirac fermions in four dimensions. This theory serves as the microscopic origin for composite Higgs models with $SU(4)/Sp(4)$ coset, supplemented by partial top compositeness. We study numerically its lattice realisation, and couple the fundamental plaquette action to Wilson-Dirac fermions in mixed representations, by adopting a (rational) hybrid Monte Carlo method, to perform non-trivial tests of the properties of the resulting lattice theory. We find evidence of a surface (with boundaries) of first-order bulk phase transitions in the three-dimensional space of bare parameters (one coupling and two masses). Explicit evaluation of the Dirac eigenvalues confirms the expected patterns of global symmetry breaking. After investigating finite volume effects in the weak-coupling phase of the theory, for the largest available lattice we study the mass spectra of the lightest spin-0 and spin-1 flavoured mesons composed of fermions in each representation, and of the lightest half-integer spin composite particle made of fermions in different representations -- the chimera baryon. This work sets the stage for future systematical studies of the non-perturbative dynamics in phenomenologically relevant regions of parameter space.

Tetravalent Doping in Fluorite-Based Ferroelectric Oxides for Reduced Voltage Operations.

First-principles calculations show a reduced energy barrier for polarization switching via a bulk phase transition by doping of hafnium-zirconium oxide (HZO). The tetragonal P42/nmc phase serves as a transition state for polarization switching of the polar orthorhombic Pca21 phase. Due to the high symmetry of the tetragonal phase, dopants can form more energetically favorable local oxygen bonding configurations in the tetragonal phase versus the orthorhombic phase. Significant bond strain is observed in the orthorhombic phase due to the low symmetry of the host crystal structure which decreases the relative stability of the doped orthorhombic phase compared to the doped tetragonal phase, thereby significantly lowering the barrier for switching but slightly affecting the polarization of the orthorhombic phase. Si is a promising dopant for an efficient ferroelectric device with minimal disturbance in the electronic structure parameters. Ge doping is suitable for stabilizing the tetragonal phase which shows a high k value.

Bulk and boundary quantum phase transitions in a square Rydberg atom array

Motivated by recent experimental realizations of exotic phases of matter on programmable quantum simulators, we carry out a comprehensive theoretical study of quantum phase transitions in a Rydberg atom array on a square lattice, with both open and periodic boundary conditions. In the bulk, we identify several first-order and continuous phase transitions by performing large-scale quantum Monte Carlo simulations and develop an analytical understanding of the nature of these transitions using the framework of Landau-Ginzburg-Wilson theory. Remarkably, we find that under open boundary conditions, the boundary itself undergoes a second-order quantum phase transition, independent of the bulk. These results explain recent experimental observations and provide important insights into both the adiabatic state preparation of novel quantum phases and quantum optimization using Rydberg atom array platforms.

Unveiling the Molecular Origin of Vapor-Liquid Phase Transition of Bulk and Confined Fluids

At temperatures below the critical temperature, discontinuities in the isotherms are one critical issue in the design and construction of separation units, affecting the level of confidence for a prediction of vapor–liquid equilibriums and phase transitions. In this work, we study the molecular mechanisms of fluids that involve the vapor–liquid phase transition in bulk and confinement, utilizing grand canonical (GCE) and meso-canonical (MCE) ensembles of the Monte Carlo simulation. Different geometries of the mesopores, including slit, cylindrical, and spherical, were studied. During phase transitions, condensation/evaporation hysteretic isotherms can be detected by GCE simulation, whereas employing MCE simulation allows us to investigate van der Waals (vdW) loop with a vapor spinodal point, intermediate states, and a liquid spinodal point in the isotherms. Depending on the system, the size of the simulation box, and the MCE method, we are able to identify three distinct groups of vdW-type isotherms for the first time: (1) a smooth S-shaped loop, (2) a stepwise S-shaped loop, and (3) a stepwise S-shaped loop with just a vertical segment. The first isotherm type is noticed in the bulk and pores having small box sizes, in which vapor and liquid phases are close and not clearly identified. The second and the third types occurred in the bulk, cylindrical, and slit mesopores with sufficiently large spaces, where vapor and liquid phases are distinctly separated. Results from our studies provide an insight analysis into vapor–liquid phase transitions, elucidating the effect of the confinement of fluid behaviors in a visual manner.

Syntheses, crystallographic characterization, and structural relations of Rb[SCN

Abstract Colorless rubidium thiocyanate was synthesized by three different approaches. DCS-TGA measurements allowed for extraction of phase transition, melting, and decomposition temperatures. Single-crystal X-ray diffraction showed Rb[SCN] to crystallize in the low-temperature LT-K[SCN] crystal structure type (Pbcm, oP16). Above its phase-transition temperature (432.1 K) the title compound crystallizes with the high-temperature HT-K[SCN] crystal structure type (I4/mcm, tI28) with head-to-tail disordered thiocyanate anions. Both modifications are related to one another and to the LT/HT-Cs[SCN] structure types, and the relation has been studied in detail employing the Bärnighausen formalism. Phase purity and bulk phase transition were confirmed by temperature-dependent PXRD.