Low-temperature X-ray Diffraction Research Articles

Terahertz fingerprint reveals the effect of alcohols on sodium ions hydration shell.

Ion hydration plays a crucial role in numerous fundamental processes. Various spectroscopic methods are employed to investigate the slowing down of hydration bond dynamics in the proximity of both anions and cations. To date, most of these studies have primarily focused on the properties of binary systems. However, in comparison to ion-water binary systems, ternary systems that involve ions, water, and organic matter are more prevalent in nature and provide more realistic insights into biological processes. This study focuses on ion hydration in water and alcohol mixture using terahertz spectroscopy and x-ray diffraction (XRD). The results reveal a distinct behavior depending on the type of alcohol used. Specifically, the presence of both methanol and ethanol results in the disappearance of absorption peaks associated with NaCl hydrate at low temperatures. In contrast, tert-butanol does not exhibit such an effect, and isopropanol demonstrates a more complex response. By combining these terahertz spectroscopic findings with low-temperature XRD data, we gain insights into the formation, or lack thereof, of NaCl · 2H2O hydrate crystals. Crucially, our observations suggest a dominant correlation between the polarity of the alcohol molecules and its impact on the Na+ hydration. Strongly polar alcohols preferentially solvating the Na+ ion lead to the failure of hydrate formation, while weakly polar alcohols do not have this effect.

Negative thermal expansion of β-Rb<sub>2</sub>SO<sub>4</sub>

Research subject. The low-temperature modification of β-Rb2SO4 sulfate (Pmcn). Aim. Low-temperature study of the thermal expansion of β-Rb2SO4 by high-temperature powder X-ray diffraction in comparison with the crystal structure, as well as interpretation of the anisotropy of β-Rb2SO4 thermal expansion. Materials and Method. Powder X-ray diffraction and high-temperature powder X-ray diffraction. Results. The thermal expansion of β-Rb2SO4 sulfate was studied for the first time using low-temperature powder thermal X-ray diffraction in comparison with the crystal structure. The phase composition was confirmed by powder X-ray diffraction. The thermal expansion of β-Rb2SO4 is practically isotropic. Across the temperature range from –177 to –140°C, the sulfate experiences negative thermal expansion. A further increase in temperature leads to a change in its thermal expansion, which becomes positive. It is proposed to consider the crystal structure of β-Rb2SO4 sulfate as a mixed framework of [RbSO4]–1, which, in turn, consists of fundamental building units (microblocks) of Rb(SO4)6. Across the temperature range from room temperature to –100°C, the maximum expansion of β-Rb2SO4 sulfate occurs along the a axis. The minimum thermal expansion is observed along the c-axis, along the columns consisting of microblocks (αa = 65.4(3)∙10–6°C–1, αb = 59.7(2)∙10–6°C–1, αc = 58.6(2)∙10–6°C–1 at +25°C). In the temperature range from –177 to –140°C, thermal expansion is negative in all three directions (αa = –10.3(3)∙10–6°C–1, αb = –8.6(2)∙10–6°C–1, αc = –9.7(2)∙10–6°C–1 at –170°C). Conclusion. The thermal expansion of β-Rb2SO4 sulfate in the low-temperature range (from –177 to –25°C) was studied for the first time, its structural interpretation was performed. A comparison was given with the thermal expansion of isostructural β-K2SO4.

Impact of crystal and molecular structure of three novel thiosulfonate crystals on their vibrational and NMR parameters

Due to antimicrobial potential of S-containing compounds, the current study explores experimentally the crystal and molecular structure of three new thiosulfonates at 100 K, notably S-ethyl 4-aminobenzene-1-sulfonothioate (1), S-ethyl 4-acetamidobenzene-1-sulfonothioate (2), and S-methyl 4-acetamidobenzene-1-sulfonothioate (3). Theoretical analysis between their molecular structure and vibrational IR, Raman, as well as NMR parameters is given. The details of -SO2-S- structural motif are analyzed theoretically using HOOH, HS-SH and H3CS-SCH3, as model molecules. The experimental structural parameters, as determined by low temperature X-ray diffraction method are accurately predicted using DFT-B3LYP combined with large and flexible aug-cc-pVTZ basis set. In case of C-S-S-C dihedral angle the crystal forces are responsible for larger difference with respect to isolated molecules, predicted in the gas phase. In addition, electronic properties of the title compounds are explored using theoretical calculations of their geometric and magnetic aromaticity indexes and substituent push-pull effect. The obtained results provide a deeper insight into their molecular structure and IR/Raman and NMR spectroscopic properties. Finally, these compounds could be directly used in future in vitro investigation of therapeutic potential of the studied and structurally similar compounds.

Structure Responsible for the Superconducting State in La3Ni2O7 at High-Pressure and Low-Temperature Conditions.

Very recently, a new superconductor with Tc = 80 K has been reported in nickelate (La3Ni2O7) at around 15-40 GPa conditions (Nature, 621, 493, 2023), which is the second type of unconventional superconductor, besides cuprates, with Tc above liquid nitrogen temperature. However, the phase diagram plotted in this report was mostly based on the transport measurement under low-temperature and high-pressure conditions, and the assumed corresponding X-ray diffraction (XRD) results were carried out at room temperature. This encouraged us to carry out in situ high-pressure and low-temperature synchrotron XRD experiments to determine which phase is responsible for the high Tc state. In addition to the phase transition from the orthorhombic Amam structure to the orthorhombic Fmmm structure, a tetragonal phase with the space group of I4/mmm was discovered when the sample was compressed to around 19 GPa at 40 K where the superconductivity takes place in La3Ni2O7. The calculations based on this tetragonal structure reveal that the electronic states that approached the Fermi energy were mainly dominated by the eg orbitals (3dz2 and 3dx2-y2) of Ni atoms, which are located in the oxygen octahedral crystal field. The correlation between Tc and this structural evolution, especially Ni-O octahedra regularity and the in-plane Ni-O-Ni bonding angles, is analyzed. This work sheds new light to identify what is the most likely phase responsible for superconductivity in double-layered nickelate.

Microscopic mechanism of carbon oxides formation during long-flame coal oxidation at molecular scale

Precursors of carbon oxides in coals are considered to be related to aldehyde group(–CHO) and carboxyl group (–COOH), but the way of decomposition of precursors to produce carbon oxides is not clear. Through theoretical analysis, experimental research and quantum chemical calculation at molecular scale, this paper explores the decomposition mode and products of carbon oxide precursors during coal spontaneous combustion (CSC). A programmed heating device was used to investigate the change rule of gas product concentration during the constant temperature oxidation of coals, and the microstructure of the coals was characterized by low-temperature nitrogen adsorption experiments (BET), X-ray Diffraction (XRD) and X-ray photoelectron spectrometer (XPS). The results of the study show that during coal oxidation, the inhomogeneous energy exchange between the coals and the external heat source results in the change of gas product concentration with time following two rules. BET experiments reveal that oxidation leads to the evolution of fine mesopores to macropores and an increase in the number of pores with diameters larger than 20 nm in the coals, which facilitates the transport of oxygen molecules through the pore structure. Within 200 °C, the microcrystalline structure of coals is basically unchanged, and the active structure C–C/C–H on the side chain is converted to –CHO and –COOH and then decomposed to produce carbon oxides. Quantum chemical calculation shows that the reaction energy barrier of carbonyl group and carboxyl group decomposed step by step to form carbon oxides is much smaller than that of direct decomposition, and carbon oxides and alkyl radicals can be produced even at room temperature by step decomposition. The research results provide theoretical guidance for the formation mechanism of carbon oxides during low temperature oxidation of coals.

Chromium(VI) Oxyfluoride Dianions, [Cr2 O4 F6 ]2- and [CrO2 F4 ]2- ; Syntheses and Structures of [XeF5 ]2 [Cr2 O4 F6 ], [XeF5 ]2 [Cr2 O4 F6 ] ⋅ nX (X=HF, n=4; X=XeOF4 , n=2), and [XeF5 ][Xe2 F11 ][CrO2 F4

The fluorobasic character of the strong oxidative fluorinator, XeF6 , and the oxidative resistance of the [XeF5 ]+ and [Xe2 F11 ]+ cations have been exploited for the syntheses of several novel Cr(VI) dianion salts. The reactions of XeF6 and CrO2 F2 in anhydrous HF and by direct fusion of the reactants in melts have yielded the first dinuclear Cr(VI) oxyfluoro-dianion salts, [XeF5 ]2 [Cr2 O4 F6 ], [XeF5 ]2 [Cr2 O4 F6 ] ⋅ 4HF, [XeF5 ]2 [Cr2 O4 F6 ] ⋅ 2XeOF4 , and mononuclear Cr(VI) oxyfluoro-dianion salt, [XeF5 ][Xe2 F11 ][CrO2 F4 ]. The salts were structurally characterized by low-temperature (LT) single-crystal X-ray diffraction (SCXRD) and LT Raman spectroscopy. The [CrO2 F4 ]2- and [Cr2 O4 F6 ]2- dianions have distorted octahedral cis-dioxo Cr(VI) coordination spheres in which two F-atoms are trans to one another and two F-atoms are trans to O-atoms, where the [Cr2 O4 F6 ]2- dianion is the fluorine-bridged dimer of the [CrO2 F3 ]- anion. Quantum-chemical calculations were used to obtain the energy-minimized, gas-phase geometries, and the calculated vibrational spectra of the gas-phase dianions and their ion-pairs, which were used to aid in the vibrational frequency assignments of the crystalline salts. NBO and MEPS analyses and SCXRD show these salts are comprised of intimate ion-pairs in which their cations and anions interact through primarily electrostatic Xe- - -F σ-hole bonds.

Crystal chemistry and predicted ionic conductivity of hydrothermally synthesized Na9Zn2(PO4)4Cl

Single crystals of sodium zincophosphate chloride were obtained under medium-temperature hydrothermal conditions and its crystal structure was determined using low temperature X-ray diffraction.

Formation of Domains within a Lower-to-Higher Symmetry Structural Transition in CrI3.

CrI3 represents one of the most important van der Waals systems on the route to understanding 2D magnetic phenomena. Being arranged in a specific layered structure, it also provides a unique opportunity to investigate structural transformations in dimension-confined systems. CrI3 is dimorphic and possesses a higher symmetry low-temperature phase, which is quite uncommon. It contrasts with vanadium trihalides, which show a higher symmetry high-temperature phase. An explanation of this distinct behavior, together with a large cycle-dependent transition hysteresis, is still an open question. Our low-temperature X-ray diffraction study conducted on CrI3 single crystals complemented by magnetization and specific heat measurements was focused mainly on specific features of the structural transition during cooling. Our results manifest that the structural transition during cooling relates to the formation of structural domains despite the lower symmetry structure transforming to a higher symmetry one. We propose that these domains could control the size of thermal hysteresis.

Unraveling concentration-dependent solvation structures and molecular interactions in water-in-salt electrolytes for enhanced performance of electric double-layer capacitors

Water-in-salt electrolytes (WiSEs) are increasingly recognized as advanced aqueous electrolytes for energy storage due to their inherent safety, wide electrochemical stability window (ESW) beyond 1.23 V, and relatively high ionic conductivity to viscosity ratio. Despite these advantages, a comprehensive understanding of the physicochemical and structural properties of WiSEs across a broad temperature spectrum remains elusive, thus limiting potential performance enhancements. In this study, the microscopic ion-ion and ion-water interactions in WiSE with potassium acetate (KOAc) as a model electrolyte were systematically analyzed in both bulk phase and electric double-layer (EDL). Concentration-dependent solvation structures, thermal and structural behaviors, and ionic transport properties were investigated through Raman spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and analytical electrochemistry measurements. The phase diagram of the aqueous KOAc solution was constructed using low-temperature XRD to identify the solidified phases, and DSC was used to determine the phase transition temperatures in a wide temperature range from -120 °C to 80 °C. We also explored the temperature-dependent electrochemical performance of various concentrations of KOAc electrolytes, finding the 5 m KOAc shows optimal performance for EDLCs at room temperature and in sub-zero temperatures. Additionally, we proposed a novel concept of an optimal cutoff voltage for maximizing power, comparing it with other commonly used metrics for setting cutoff voltage. This study validates our approach and highlights its significance in balancing key performance parameters.

Unveiling the structural phase transition and magnetic structure of ternary boride PrIr3B2

We present a comprehensive study of PrIr3B2, which includes a detailed investigation of its crystal and magnetic structure using neutron diffraction. AC and DC magnetization and heat capacity data reveal antiferromagnetic ordering at T N = 10 K. The heat capacity measurements further exhibit a broad peak near 270 K which is related to a structural transition from P6/mmm to C2/m seen in low temperature x-ray diffraction and neutron diffraction. High intensity neutron diffraction data confirm the long-range ordering of Pr3+ spins, with no apparent magnetic moment on either of the Iridium sites. Two possible magnetic structures with either k 1 = [1,0,0] or k 2 = [½,½,0] fit nearly equally well the neutron diffraction data. However, based on previous magnetization studies on a single crystalline sample it is argued that the second solution with k 2 corresponds to the appropriate magnetic structure of PrIr3B2 below 10 K. In this magnetic structure, the Pr3+ moments are oriented at ∼45° to both the a and b axes, with the c-axis being the hard axis of magnetization. Overall, our results provide new insights into the magnetic and structural properties of PrIr3B2.

Thermal expansion behavior of vanadium pernitride, CuAl2-type VN2, synthesized under high pressures

CuAl2-type VN2, which is synthesized under high pressure, is a recoverable material at ambient conditions and has a high bulk modulus. In this study, we investigated the thermal expansion behavior of CuAl2-type VN2 by low-temperature X-ray diffraction measurements between 109.3(5) K and 298.3(8) K. The axial thermal expansion coefficient of VN2 was determined to be αa = 2.7(9) × 10−6 K−1 and αc = 17.8(12) × 10−6 K−1 at 298.3(8) K, which has large anisotropy similar to that of compression behavior. It is found that the small coefficient of thermal expansion of the a-axis is due to the negative and positive effects on the a-axis length with increasing temperature of the bond angles and bond lengths of VN2, respectively. As a result, VN2 exhibits very large anisotropic thermal expansion behavior.

3-Nitro-benzo-nitrile.

The crystal structure of 3-nitrobenzonitrile, C7H4N2O2, was elucidated by low-temperature single-crystal X-ray diffraction. The compound crystallizes in the Sohncke space group P21 and features two mol-ecules in the unit cell. Aromatic π-π stacking leads to stacks of mol-ecules in the [100] direction. The absolute structure was established from anomalous dispersion.

Effect of the Pore Structure of Nanosilicas Decorated with Cobalt and Cerium Oxides on Catalytic Activity in the Selective Oxidation of Carbon Monoxide

Two types of nanosilicas with different pore structures are synthesized and decorated via impregnation with cobalt and cerium oxides. Meso–microporous spherical silica particles with thin walls of SiO2 nanochannels having specific surface area and pore volume of up to 1400 m2/g and 0.8 cm3/g, respectively, are used. Macroporous three-dimensionally ordered structures based on SiO2 (so-called synthetic opals) consisting of close-packed submicron spherical silica particles with respective porosity characteristics of 11 m2/g and 0.2 cm3/g are also used. The synthesized materials are characterized via low-temperature nitrogen adsorption, X-ray diffraction, SEM, XPS, and Fourier transform IR spectroscopy, and tested as catalysts for the selective oxidation of CO in excess H2 (CO-PROX). The effect of silica, the ratio of introduced oxides, and the order of their introduction on the structure and catalytic properties of Co–Ce/SiO2 are revealed. The catalytic behavior of the synthesized materials is determined from the specificity of interactions among the metal oxides and with the silica surface.

Mineralogical Characteristics and Arsenic Release of High Arsenic Coals from Southwestern Guizhou, China during Pyrolysis Process

Coal is the primary energy source in China, and coal pyrolysis is considered an essential and efficient method for clean coal utilization. Three high arsenic coals collected from the southwestern Guizhou province of China were chosen in this study. Low-temperature ashing plus X-ray diffraction analysis (XRD) was used to identify the minerals in coals. The three coals were pyrolyzed in a tube furnace in an N2 atmosphere at 950 °C, 1200 °C, and 1400 °C, respectively. Environment scanning electron microscope (ESEM), XRD, X-ray fluorescence analysis (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS) were adopted to determine the morphology, mineral compositions, and element compositions and arsenic contents of the coal pyrolysis ashes, respectively. It can be found that minerals in coal are mainly composed of quartz, pyrite, muscovite, and rutile. The minerals in the ashes generated from coal pyrolysis mainly contain quartz, dehydroxylated muscovite, iron oxide minerals, mullite, and silicon nitride. Oldhamite and gupeite exist at 950 °C and 1400 °C, respectively. The morphologies of oldhamite and gupeite at these temperatures are irregular block-shaped particles and irregular spherical particles, respectively. The mineralogical transformations in the process of coal pyrolysis affect coal utilization. The arsenic release rate is higher than 87% during pyrolysis at 1400 °C. The arsenic in organic matter is more able to be volatilized than mineral components. The retention time can slightly influence the arsenic release rate, and the influence of temperature is much more significant than the influence of retention time. The understanding of mineral evolution and arsenic environmental emission is helpful for the safety of high-arsenic coal pyrolysis.

Thermodynamic and High-Temperature Properties of KFe0.33W1.67O6

This paper presents the results of a study of the KFe0.33W1.67O6 system. The compound was obtained by a solid-phase synthesis method at a temperature of 1073 K. The structural, morphological, and spectroscopic properties of KFe0.33W1.67O6 were characterized using XRD, SEM-EDS. The compound crystallizes in a cubic lattice with the space group Fd–3m (227). The obtained lattice parameter a = 10.3697 (3) Å. The phase transitions of KFe0.33W1.67O6 were determined by low-temperature and high-temperature X-ray diffraction. The temperature dependence of heat capacity of KFe0.33W1.67O6 has been measured for the first time in the range from 5 to 638 K by precision adiabatic vacuum calorimetry and differential scanning calorimetry. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity C∘p∘(T), enthalpy H°(T) − H°(0), entropy S°(T) − S°(0), and Gibbs function G°(T) − H°(0), for the range from T → 0 to 630 K.

Synthesis, structure, ADME and biological activity of three 2,6-disubstituted thiosemicarbazone derivatives.

Three new 2,6-disubstituted thiosemicarbazone derivatives of pyridine, namely, 2-{amino[6-(pyrrolidin-1-yl)pyridin-2-yl]methylidene}-N,N-dimethylhydrazine-1-carbothioamide, C13H20N6S, 2-{amino[6-(piperidin-1-yl)pyridin-2-yl]methylidene}-N,N-dimethylhydrazine-1-carbothioamide, C14H22N6S, and 2-[amino(6-phenoxypyridin-2-yl)methylidene]-N,N-dimethylhydrazine-1-carbothioamide monohydrate, C15H17N5OS·H2O, have been synthesized and characterized by NMR spectroscopy and low-temperature single-crystal X-ray diffraction. In addition, their antibacterial and anti-yeast activities have been determined. The ability of the tested compounds to inhibit bacterial growth was comparable to vancomycin as a reference drug. Compared to isoniazid (MIC 0.125 and 8 µg ml-1), the compounds showed the ability to inhibit the growth of Mycobacterium tuberculosis to a moderate degree for the standard strain and at the same level or higher (MIC 4-8 µg ml-1) for the resistant strain. All three compounds adopt the zwitterionic form in the crystal structure regardless of the presence or absence of solvent molecules.

Magnetic ordering in terbium at high pressures and low temperatures

We have investigated magnetic ordering in the heavy lanthanide terbium (Tb) for pressures up to 70 GPa and temperatures down to 20 K by synchrotron x-ray diffraction at the Advanced Photon Source, Argonne National Laboratory. The x-ray diffraction studies were complemented by neutron diffraction studies at the Spallation Neutron Source, Oak Ridge National Laboratory. We focused on the higher-pressure phases of Tb, such as the double hexagonal close-packed (dhcp, above 16 GPa), distorted face-centered cubic (hR24, above 30 GPa), and orthorhombic (oF16, above 51 GPa) phases. We observed the phenomenon of spontaneous magnetostriction in the dhcp and hR24 phases, where magnetic ordering at low temperatures gives rise to subtle splitting in x-ray diffraction peaks. The neutron diffraction study of the dhcp phase at 20 GPa revealed magnetic peaks that can be assigned a propagation vector k=(12,0,12), and a magnetic ordering temperature that is consistent with the magnetostriction effect observed with x-ray diffraction. The high-pressure and low-temperature x-ray diffraction study at 70 GPa in the collapsed oF16 phase did not show any evidence of magnetostriction, indicating a significant decrease in the magnetic moment of the 4f-shell due to band broadening at ultra-high compression.

High-Temperature Behavior of Laser Electrodispersion-Prepared Pd/ZSM-5 Hydrocarbon Traps under CO Oxidation Conditions.

Zeolites and metal-doped zeolites are now widely considered as low-temperature hydrocarbon traps to be a part of emission control systems in automobiles. However, due to the high temperature of exhaust gases, the thermal stability of such sorbent materials is of great concern. To avoid the thermal instability problem, in the present work, laser electrodispersion was used to deposit Pd particles on the surface of ZSM-5 zeolite grains (SiO2/Al2O3 = 55 and SiO2/Al2O3 = 30) to obtain Pd/ZSM-5 materials with a Pd loading as low as 0.03 wt.%. The thermal stability was evaluated in a prompt thermal aging regime involving thermal treatment at temperatures up to 1000 °C in a real reaction mixture (CO, hydrocarbons, NO, an excess of O2, and balance N2) and a model mixture of the same composition with the exception of hydrocarbons. Low-temperature nitrogen adsorption and X-ray diffraction analysis were used to examine the stability of the zeolite framework. Special attention was paid to the state of Pd after thermal aging at varied temperatures. By means of transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance UV-Vis spectroscopy, it was shown that palladium, having been initially located on the surface of zeolite, undergoes oxidation and migrates into the zeolite's channels. This enhances the trapping of hydrocarbons and their subsequent oxidation at lower temperatures.

Uncovering Multiple Intrinsic Chiral Phases in (PEA)2PbI4 Halide Perovskites.

Two-dimensional (2D) halide perovskites offer a unique platform for investigating the ground state of materials possessing significant anharmonicity. In contrast to three-dimensional perovskites, their 2D counterparts offer substantially fewer degrees of freedom, resulting in multiple well-defined crystal structures. In this work, we thoroughly investigate the anharmonic ground state of the benchmark (PEA)2PbI4 compound, using complementary information from low-temperature X-ray diffraction (XRD) and photoluminescence spectroscopy, supported by density functional theory calculations. We extrapolate four crystallographic configurations from low-temperature XRD. These configurations imply that the ground state has an intrinsic disorder stemming from two coexisting chiral sublattices, each with a bioriented organic spacer molecule. We further show evidence that these chiral structures form unevenly populated ground states, portraying uneven anharmonicity, where the state population may be tuned by surface effects. Our results uncover a disordered ground state that may induce intrinsic grain boundaries, which cannot be ignored in practical applications.

Application of 1- and 2-propargyl-tetrazole in laser-ignitable energetic coordination compounds

1- and 2-Propargyl-tetrazole (1- and 2-PryTz) were synthesized by reaction of propargyl bromide with sodium tetrazolate and used as ligands in energetic coordination compounds (ECCs) and evaluated concerning their thermal and mechanical sensitivities. Furthermore, the two nitrogen-rich compounds 1-((1H-1,2,3-triazol-4-yl)methyl)-1H-tetrazole (TriMT, 3) and 1-((1-(2-(1H-tetrazol-1-yl)ethyl)-1H-1,2,3-triazol-4-yl)methyl)-1H-tetrazole (TriMTET, 4) were prepared. Both were characterized by IR spectroscopy, NMR measurements, and low-temperature X-Ray diffraction analysis. Due to the highly endothermic enthalpy of formation of the propargyl-tetrazole ligands, powerful, yet relatively safe to handle, laser-ignitable ECCs were obtained.