X-ray Powder Diffraction Experiments Research Articles

A multipurpose laboratory diffractometer for operando powder X-ray diffraction investigations of energy materials.

Laboratory X-ray diffractometers are among the most widespread instruments in research laboratories around the world and are commercially available in different configurations and setups from various manufacturers. Advances in detector technology and X-ray sources push the data quality of in-house diffractometers and enable the collection of time-resolved scattering data during operando experiments. Here, the design and installation of a custom-built multipurpose laboratory diffractometer for the crystallographic characterization of battery materials are reported. The instrument is based on a Huber six-circle diffractometer equipped with a molybdenum microfocus rotating anode with 2D collimated parallel-beam X-ray optics and an optional two-bounce crystal monochromator. Scattered X-rays are detected with a hybrid single-photon-counting area detector (PILATUS 300K-W). An overview of the different diffraction setups together with the main features of the beam characteristics is given. Example case studies illustrate the flexibility of the research instrument for time-resolved operando powder X-ray diffraction experiments as well as the possibility to collect higher-resolution data suitable for diffraction line-profile analysis.

Single-Phase Precursors for the Preparation of Spinel Ferrites via Oxalate Route: the Study of Cobalt Ferrite Synthesis.

This work explores the benefits of single-phase oxalate precursors for the preparation of spinel ferrites by thermal decomposition. A direct comparison between the genuine oxalate solid solution and the physical mixture of simple oxalates is presented using the case study of cobalt ferrite preparation. The mixing of metal cations within a single oxalate structure could be verified prior to its thermal decomposition by several non-destructive experimental techniques, namely Mössbauer spectroscopy, X-ray powder diffraction (XRD) and energy-dispersive X-ray spectroscopy. In situ XRD experiments were conducted to compare the decomposition processes of the solid solution and the physical mixture. Additionally, the decomposition products of the FeCo oxalate solid solution were studied ex situ by means of N2 adsorption, Mössbauer spectroscopy and XRD. The results obtained for different reaction temperatures demonstrate the possibilities to easily control the physical properties of the prepared oxides.

High-pressure structure of praseodymium revisited: In search of a uniform structural phase sequence for the lanthanide elements

Angle-dispersive x-ray powder diffraction experiments have been performed on praseodymium metal to a pressure of 205 GPa. Between 20 and 165 GPa only the $oC4$ ($\ensuremath{\alpha}$-uranium) phase is observed, in agreement with previous studies. At 171(5) GPa we find a transition to a tetragonal $tI2$ phase which is isostructural with the high-pressure post-$oC4$ phase seen in the neighboring lanthanide cerium above 12 GPa, and with the high-pressure phase of the actinide thorium seen above 100 GPa. Electronic structure calculations determine the $oC4\ensuremath{\rightarrow}tI2$ transition to occur at 130 GPa at 0 K, but find another phase, with the $hP1$ (simple hexagonal) structure, to have a lower enthalpy than both the $oC4$ and $tI2$ structures above 20 GPa at 0 K.

Paper mill sludge-based carbon quantum dots as a specifically ratiometric fluorescent probe for the sensitive and selective detection of coptisine.

Coptisine (COP), one of the bioactive components in Rhizoma Coptidis, has many pharmacological effects. Meanwhile, the determination of COP is essential in pharmacological and clinical applications. Herein, we prepared carbon quantum dots (CQDs) by one-step oil-thermal method using paper mill sludge (PMS) as precursor, and developed a ratiometric fluorescence method for the determination of COP. The structural and optical properties of PMS-CQDs were evaluated through high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), ultraviolet-visible (UV-vis), fluorescence, zeta potential and fluorescence lifetime experiments. Fluorescence intensity ratio at 550 nm and 425 nm (I550 /I425 ) was recorded as an index for quantitative detection of COP. The detection concentration of COP ranges from 0.1 to 50 μM in good linear correlation (R2 =0.9974) with a limit of detection of 0.028 μM (3σ/k). The quenching mechanism was deduced to be inner filter effect and static quenching. The ratiometric fluorescent probe showed impressive selectivity and sensitivity towards COP, and was successfully applied to the detection of COP in human urine with expected recoveries (95.22-111.00%) and relative standard deviations (0.46-2.95%), indicating that our developed method has a great application prospect in actual sample detection.

Systematic structural study in praseodymium compressed in a neon pressure medium up to 185 GPa

Angle-dispersive x-ray powder diffraction experiments have been performed on praseodymium metal compressed in a soft pressure-transmitting medium at ambient temperature up to 185 GPa. We observe the previously reported high-pressure structural transition sequence up to 20 GPa and the coexistence of body-centered orthorhombic (bco) Pr and \ensuremath{\alpha}-U Pr from $\ensuremath{\sim}20$ up to $\ensuremath{\sim}38\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$. The \ensuremath{\alpha}-U structure of Pr is stable from 20 to 185 GPa, and no evidence of the proposed transition to a primitive orthorhombic phase $>147\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$ was observed. With density functional theory (DFT), we calculated the lattice parameters and $y$ coordinate for \ensuremath{\alpha}-U Pr and found good agreement between our calculations and experimental measurements. The obtained DFT energies of the proposed primitive orthorhombic $(P{2}_{1}{2}_{1}{2}_{1})$ and the \ensuremath{\alpha}-uranium phases at $\ensuremath{\sim}150\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$ show that the \ensuremath{\alpha}-uranium phase is lower in energy. Hence, neither our experimental data nor our DFT results support the transition to a primitive orthorhombic phase $>150\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$. DFT suggests, however, that Pr may transform to the $P{2}_{1}{2}_{1}{2}_{1}$ phase above $\ensuremath{\sim}220\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$. We also compare the axial ratios and lattice parameters of praseodymium to \ensuremath{\alpha}-uranium structured Nd, Ce, and U.

Ni4-thiacalix[4]arene sandwiched Mo8 polyoxometalate bimetallic nanoclusters for electrocatalytic glucose oxidation

Available online two new Ni8Mo8 bimetallic coordination clusters, [Ni4(TC4A)]2[(Mo5VMo3VIO24)(PO4)] (+Solvent) (Ni8PMo8, H4TC4A= p-tert-butylthiacalix[4]arene) and [Ni4(TC4A)]2[(Mo5VMo3VIO24)(OH)(CO3)] (+Solvent) (Ni8Mo8), were synthesized by solvothermal method and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, FT-IR spectroscopy, and TGA experiments, respectively. The usage of H3PMo12O40 as source for Ni8PMo8 resulted a sandwich like structure built from two Ni4-thiacalix[4]arene units and a Mo8 polyoxometalate with inner spaces of PO43−. Ni8Mo8 with the similar structure to that of Ni8PMo8 is from H2MoO4 starting reagent with OH− and CO32− anions encapsulated in the center. The two clusters can be directly loaded on carbon paper and utilized as working electrodes which showed distinguishable performances for glucose detection and oxidation. This work provides a better understanding of the structure–property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building calixarene-based or polyoxometalate-based functional materials.

Combination of Knoevenagel Polycondensation and Water-Assisted Dynamic Michael-Addition-Elimination for the Synthesis of Vinylene-Linked 2D Covalent Organic Frameworks.

Vinylene‐linked two‐dimensional conjugated covalent organic frameworks (V‐2D‐COFs), belonging to the class of two‐dimensional conjugated polymers, have attracted increasing attention due to their extended π‐conjugation over the 2D backbones associated with high chemical stability. The Knoevenagel polycondensation has been demonstrated as a robust synthetic method to provide cyano (CN)‐substituted V‐2D‐COFs with unique optoelectronic, magnetic, and redox properties. Despite the successful synthesis, it remains elusive for the relevant polymerization mechanism, which leads to relatively low crystallinity and poor reproducibility. In this work, we demonstrate the novel synthesis of CN‐substituted V‐2D‐COFs via the combination of Knoevenagel polycondensation and water‐assisted dynamic Michael‐addition‐elimination, abbreviated as KMAE polymerization. The existence of C=C bond exchange between two diphenylacrylonitriles (M1 and M6) is firstly confirmed via in situ high‐temperature NMR spectroscopy study of model reactions. Notably, the intermediate M4 synthesized via Michael‐addition can proceed the Michael‐elimination quantitatively, leading to an efficient C=C bond exchange, unambiguously confirming the dynamic nature of Michael‐addition‐elimination. Furthermore, the addition of water can significantly promote the reaction rate of Michael‐addition‐elimination for highly efficient C=C bond exchange within 5 mins. As a result, the KMAE polymerization provides a highly efficient strategy for the synthesis of CN‐substituted V‐2D‐COFs with high crystallinity, as demonstrated by four examples of V‐2D‐COF‐TFPB‐PDAN, V‐2D‐COF‐TFPT‐PDAN, V‐2D‐COF‐TFPB‐BDAN, and V‐2D‐COF‐HATN‐BDAN, based on the simulated and experimental powder X‐ray diffraction (PXRD) patterns as well as N2‐adsorption–desorption measurements. Moreover, high‐resolution transmission electron microscopy (HR‐TEM) analysis shows crystalline domain sizes ranging from 20 to 100 nm for the newly synthesized V‐2D‐COFs.

Manganese crystalline phases developed in high lead glazes during firing

A High Temperature Synchrotron Radiation X-Ray Powder Diffraction experiment was performed to determine the manganese compounds formed during the heating and cooling of 70 wt% PbO – 30 wt% SiO2 mixture or the equivalent glass plus 10 wt% of MnO. The effect of adding calcite, dolomite and kaolinite were also studied. All mixtures were fired between 690 °C and 1020 °C in oxidizing conditions and analysed by Scanning Electron Microscopy.A sequence of manganese phases are formed during firing: bixbyite (Mn2O3), barysilite ((Pb,Mn)Si2O7), kentrolite (Pb2Mn2Si2O9) and braunite (Mn7SiO12). Kentrolite and braunite crystallise with different crystal habits during the heating and the cooling. If dolomite is present diopside ((Ca,Mg,Mn)2Si2O6) is formed. If calcite is present, ganomalite (Pb3(CaMn)2Si3O11), margarosanite (Pb(Ca,Mn)2Si3O9) and wollastonite ((Ca,Mn)SiO3) are also formed. Wollastonite can incorporate enough manganese to transform into bustamite ((Mn,Ca)3Si3O9) at high temperatures. This leaves less manganese available for the crystallisation of kentrolite and braunite.

In Situ Analytical Methods for the Characterization of Mechanochemical Reactions

The interest in mechanochemical reactions and their fields of application have increased enormously in recent times. Mechanically activated reactions offer the advantage of cost-efficiency as well as environmentally friendly syntheses routes. In contrast to thermally induced processes, the energy transfer via the milling media takes place on a local scale. This leads to unique reaction pathways, which often also result in the formation of metastable phases. For the understanding of reaction pathways on a mechanistic level, it is very important to follow the processes taking place in the grinding jar during milling. Besides the measurement of pressure and temperature changes during a mechanochemical reaction, in situ high energy synchrotron X-ray powder diffraction and Raman spectroscopy experiments have been successfully implemented over the last 10 years. This review will highlight the developments which were achieved in the field of in situ monitoring of mechanochemical reactions and their input to the understanding of mechanochemistry.

Lattice distortion and magnetic property of high entropy alloys at low temperatures

Deformation mechanisms and magnetic properties of medium and high entropy alloys (MEA/HEAs) closely relate to lattice distortion and are strongly temperature-dependent, in particular, at low temperature ranges. However, little attention has been paid to the evolution of lattice distortion with temperature decreasing and its effects on deformation behavior and magnetic state transition. In this work, we carry out in situ synchrotron radiation based X-ray powder diffraction (SR-XRD) experiments from 293 to 123 K aiming for determining lattice distortion evolutions of CrCoNi MEA, CrFeCoNi and CrMnFeCoNi HEAs. Magnetic measurements at corresponding low temperatures and cryogenic ranges are further conducted. The in situ SR-XRD results demonstrate a general reduction of lattice distortion magnitude with temperature decreasing, which shows a similar tendency with that of reported stacking fault energy (SFE) values. It is thus suggested that lattice distortion reduction possibly makes a critical contribution to deformation mechanism transition. The magnetic measurement results show a clear ferromagnetic transition of CrFeCoNi HEA when temperature is below 173 K. While, no obvious magnetic state transition is observed for CrCoNi MEA and CrMnFeCoNi HEA. The present findings on lattice distortion evolutions will pave the way for designing targeted HEAs with particular properties.

Monoclinic–triclinic phase transition induced by pressure in fergusonite-type YbNbO4

We have carried out a high-pressure study on monoclinic fergusonite-type YbNbO4. Synchrotron powder x-ray diffraction experiments and density-functional theory simulations have been performed. We found a gradual increase of symmetry under compression, with calculations predicting a second-order monoclinic–tetragonal transition at 15 GPa. However, experiments provided evidence of a transition at 11.6 GPa to a triclinic structure, described by space group . The appearance of the triclinic phase, which according to calculations is dynamically unstable under hydrostatic conditions, seems to be related to the presence of non-hydrostatic stresses. The triclinic high-pressure phase remains stable up to 31.9 GPa and the phase transition is not reversible. We have determined the pressure dependence of unit-cell parameters of both phases and calculated their room-temperature equation of state. For the fergusonite-phase we have also obtained the isothermal compressibility tensor. In addition to the high-pressure studies, we report ambient-pressure Raman and infrared spectroscopy measurements which have been compared with density-functional theory calculations.

Synthesis and luminescence studies of Dy3+ doped Li3Sc(BO3)2 polycrystalline powder for warm white light

Li3Sc(BO3)2, an orthoborate polycrystalline compound, was synthesised using the solid-state synthesis method as a pure and Dy2O3-doped material. Dy3+ ions were used in various concentrations (from 1 to 6 mol. %). The experimental powder X-ray diffraction data and calculated Rietveld refined data are found to be in good agreement, verifying the effectiveness of the synthesis procedure. The luminescence studies were performed under the excitations of X-ray, proton beam, and UV light. The success of radioluminescence studies verifies the prospects of the Dy3+-doped compound for its application as a radiation scintillator in imaging. The experimental study of cross-relaxation processes confirms the lack of potential evidence of the quenching of the emission peak at 765 nm through the absorption via 6H15/2 → 6F3/2 electronic transition cross-relaxation channel −1. The CIE 1931 colour coordinates and correlated colour temperatures were determined for all doped samples under X-ray, proton beam, and photoluminescence excitations. The obtained combined emission colour appeared in the warm white region, unlike many other Dy3+-doped phosphors that suffer suppression of luminescence through the cross-relaxation process.

Development of a Method for X-ray Absorption Near-edge Spectra Measurement using Fluorescent Background in Powder X-ray Diffraction Experiments

Development of a Method for X-ray Absorption Near-edge Spectra Measurement using Fluorescent Background in Powder X-ray Diffraction Experiments

Role of rare earth sites and vacancies in the anomalous compression of modulated scheelite tungstates RE2 ( WO4)3

X-ray powder diffraction experiments at high pressures combining conventional sources and synchrotron radiation, together with theoretical simulations have allowed us to study the anomalous compression of the entire \ensuremath{\alpha}-${RE}_{2}$(${\mathrm{WO}}_{4}{)}_{3}$ ($\mathit{RE}$ = La-Ho) family with modulated scheelite structure (\ensuremath{\alpha} phase). The investigated class of materials is of great interest due to their peculiar structural behavior with temperature and pressure, which is highly sought after for specialized high-tech applications. Experimental data were analyzed using full-profile refinements and were complemented with computational methods based on density functional theory (DFT) total energy calculations for a subset of the samples investigated. An unusual change in the compression curves of the lattice parameters $a, c$, and \ensuremath{\beta} was observed in both the experiments and theoretical simulations. In particular, in all the studied compounds the lattice parameter $a$ decreased with pressure to a minimum value and then increased upon further compression. Pressure evolution of the experimental x-ray diffraction (XRD) patterns and cell parameters is correlated with the ionic radius of the rare earth element: (1) the lighter La-Nd tungstates underwent two phase transitions, and both transition pressures decreased as the rare earth's ionic radius increased. The XRD patterns of the first high pressure phase could be indexed with propagation vectors parallel to the $a$ axis (tripling the unit cell). At higher pressures, the lattice parameters for the second phase (referred to as the preamorphous phase) showed little variation with pressure. (2) The heavier tungstates, from Sm to Dy, undergo a transition to the preamorphous phase without any intermediate phase. The reversibility of both phase transitions was investigated. DFT calculations support this unusual response of the crystal structures under pressure and shed light on the structural mechanism of negative linear compressibility (NLC) and the resulting softening. The pressure dependence of the structural modifications is related to tilting, along with small elongation and alignment, of the ${\mathrm{WO}}_{4}^{2\ensuremath{-}}$ tetrahedrons. These changes correlate with those in the alternating RE\dots{}RE\dots{}RE chains and blocks of cationic vacancies arranged along the $a$ axis. Possible stacking defects, which emerge between them, helped to explain this anomalous compression and the pressure induced amorphization. Such mechanisms were compared with other ferroelastic families of molybdates, niobates, vanadates, and other compounds with similar structural motifs classified as having ``hinge frames.''

Desolvation–Solvation-Induced Reversible On–Off Switching of Two Memory Channels in a Cobalt(II) Coordination Polymer: Overlay of Spin Crossover and Structural Phase Transition

Desolvation–Solvation-Induced Reversible On–Off Switching of Two Memory Channels in a Cobalt(II) Coordination Polymer: Overlay of Spin Crossover and Structural Phase Transition

Phenothiazine-Based Luminophores with AIE, Solvatochromism, and Mechanochromic Characteristics.

Aggregation-induced emission (AIE) fluorescent molecules with unique photoelectric properties have received extensive attention due to the wide range of applications. In this work, two novel phenothiazine-based luminophores DPE-PTZ-Cl and DPE-PTZ-CF3 were designed based on the frontier molecular orbital (FMO) theory and construction strategy of AIEgens. As expected, both of the luminophores displayed typical AIE behavior and realized the spatial separation of FMOs, which was confirmed by the positive solvatochromism behavior. Their AIE properties could be attributed to the twisted three-dimensional (3D) conformation. Such a conformation resulted from "butterfly-like" phenothiazine and a multirotor structure of diphenylethylene. The spatial separation of FMOs originated from the push-pull electronic synergistic effect of the donor-acceptor (D-A) architecture. Interestingly, DPE-PTZ-Cl also showed a rare blue-shifted mechanochromic (MC) luminescence property. Single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD) experiments were carried out to reveal that the phase transformation between crystalline and amorphous states was responsible for the peculiar solid-state luminescence phenomenon.

Stoichiomorphic halogen-bonded cocrystals: a case study of 1,4-diiodotetrafluorobenzene and 3-nitropyridine

The concept of variable stoichiometry cocrystallization is explored in halogen-bonded systems. Three novel cocrystals of 1,4-diiodotetrafluorobenzene and 3-nitropyridine with molar ratios of 1:1, 2:1, and 1:2, respectively, are prepared by slow evaporation methods. Single-crystal X-ray diffraction analysis reveals key differences between each of the nominally similar cocrystals. For instance, the 1:1 cocrystal crystallizes in the P21/n space group and features a single chemically and crystallographically unique halogen bond between iodine and the pyridyl nitrogen. The 2:1 cocrystal crystallizes in the [Formula: see text] space group and features a halogen bond between iodine and one of the nitro oxygens in addition to an iodine–nitrogen halogen bond. The 1:2 cocrystal crystallizes with a large unit cell (V = 9896 Å3) in the Cc space group and features 10 crystallographically distinct iodine-nitrogen halogen bonds. Powder X-ray diffraction experiments carried out on the 1:1 and 2:1 cocrystals confirm that gentle grinding does not alter the crystal forms. 1H → 13C and 19F → 13C cross-polarization magic angle spinning (CP/MAS) NMR experiments performed on powdered samples of the 1:1 and 2:1 cocrystals are used as spectral editing tools to select for either the halogen bond acceptor or donor, respectively. Carbon-13 chemical shifts in the cocrystals are shown to change only very subtly relative to pure solid 1,4-diiodotetrafluorobenzene, but the shift of the carbon directly bonded to iodine nevertheless increases, consistent with halogen bond formation (e.g., a shift of +1.6 ppm for the 2:1 cocrystal). This work contributes new examples to the field of variable stoichiometry cocrystal engineering with halogen bonds.

Potassic-Hastingsite from the Kedrovy District (East Siberia, Russia): Petrographic Description, Crystal Chemistry, Spectroscopy, and Thermal Behavior

In this work we report on a petrographic, crystal-chemical, and optical characterization, obtained from different analytical methods, of amphibole species. Potassic-hastingsite, ideally AKBCa2C(Fe2+4Fe3+)T(Si6Al2)O22W(OH)2, has been found in the Kedrovy district (East Siberia, Russia). The sample occurs as well-formed and large radially radiant aggregates of dark green, almost black crystals. The unit cell dimensions are a = 9.9724(3) Å, b = 18.2968(4) Å, c = 5.3573(1) Å, β = 104.945(3)°, V = 944.44(4) Å3, Z = 2. Site populations were determined by combining single-crystal structure refinement and electron probe microanalysis, and Fe3+/Fe2+ ratio was obtained from X-ray fluorescence analysis. Infrared, diffuse light UV/Vis/NIR absorption, and electron spin resonance spectra are presented and discussed. A thermoelastic behavior of a powder of potassic-hastingsite was studied by in situ high-temperature X-ray diffraction. A thermal expansion and subsequent significant contraction in the unit cell volume during a high-temperature X-ray powder diffraction experiment is observed as a consequence of the deprotonation process, which is locally balanced via oxidation of Fe2+. According to the data obtained for potassic-hastingsite, these processes occur within 400–600 °C. The thermal expansion of the mineral is anisotropic; the thermal expansivity coefficients αa:αb:αc (×10−6) = −18.06:9.59:−1.09 at 400 °C, −26.15:−1.52:2.22 at 600 °C and 23.77:−25.06:42.08 at 750 °C.

Scalemic mixtures preparation for optimized composition of ibuprofen solid dosage forms

The stable and metastable phase diagrams between the sinister and the rectus ibuprofen enantiomers were established by means of thermal analysis and X-ray powder diffraction experiments as a function of temperature. The results obtained allow proving for the first time the existence, for the stable system, of a solid solution by mixing the racemic ibuprofen with one of its enantiomers for low concentration of the enantiomer. Since the rectus ibuprofen is a non-active pharmaceutical agent which can be partially bio-converted into the sinister enantiomer, the present work offers a new approach for scalemic mixtures preparation in order to improve the benefit/risk ratio related to ibuprofen solid dosage form administration.

Synthesis, crystal and electronic structure of CaNi2Al8

Abstract Single crystals of CaNi2Al8 were obtained during attempts to synthesize CaNi2Al9 from the elements in Nb or Al2O3 crucibles in an induction furnace. The orthorhombic structure of CaNi2Al8 was refined based on single-crystal X-ray diffraction data (Pbam, a = 1252.30(6), b = 1443.73(7), c = 395.78(2) pm, wR2 = 0.0423, 2225 F 2 values, 63 variables) and full atomic ordering was observed. The compositions of the samples were checked by powder X-ray diffraction experiments; no phase pure samples could be obtained. To analyze the bonding situation of the title compound in detail, quantum-chemical calculations were conducted. According to Density Functional Theory, CaNi2Al8 is a intermetallic compound with a polar covalently bonded [Ni2Al8] network showing strong Ni–Al and Al–Al bonding.