Analysis Of X-ray Diffraction Data Research Articles

Synergistic Effects of BaTiO3 and MFe2O4 (M = Mn, Ni, Cu, Zn, and Co) Nanoparticles as Artificial Pinning Centers on the Performance of YBa2Cu3Oy Superconductor.

Large-scale superconductor applications necessitate a superconducting matrix with pinning sites (PSs) that immobilize vortices at elevated temperatures and magnetic fields. While previous works focused on the single addition of nanoparticles, the simultaneous inclusion of different nanoparticles into a superconducting matrix can be an effective way to achieve an improved flux pinning capacity. The purpose of this study is to explore the influence of mixed-nanoparticle pinning, with the co-addition of non-magnetic (BaTiO3; BT) and various types of magnetic spinel ferrite (MFe2O4, abbreviated as MFO, where M = Mn, Co, Cu, Zn, and Ni) nanoparticles, on the superconductivity and flux pinning performances of the high-temperature superconductor YBa2Cu3Oy (YBCO). An analysis of X-Ray diffraction (XRD) data of BT-MFe2O4-co-added YBCO samples showed the formation of an orthorhombic structure with Pmmm symmetry. According to electrical resistivity measurements, the emergence of the superconducting state below Tcoffset (zero-resistivity temperature) was proven for all samples. The highest Tcoffset value was recorded for the Y-BT-MnFO sample, while the minimum value was obtained for the Y-BT-ZnFO sample. Direct current (DC) magnetization results showed good magnetic flux pinning performance for all the co-added samples compared to the pristine sample but with some discrepancies. At 77 K, the values of the self-critical current density (self-Jcm) and maximum pinning force (Fpmax) for the Y-BT-MnFO sample were found to be eight times higher and seventeen times greater than those for the pristine sample, respectively. The results acquired suggested that mixing the BT phase with an appropriate type of spinel ferrite nanoparticles can be a practical solution to the problem of degradation of the critical current density of the YBCO material.

Supramolecular Structure of Sulfonamide-Substituted Silatranes: Quantum Chemical DFT Calculations.

The supramolecular structure of the crystal products-N-[2-chloro-2-(silatranyl)ethyl]-4-nitro-benzenesulfonamide 4d and N-chloro-N-[2-chloro-1-(silatran-1-yl-methyl)ethyl]benzene-sulfonamide 5a was established by X-ray diffraction analysis data, FTIR spectroscopy and DFT quantum chemical calculations. Their crystal lattice is formed by cyclic dimers with intermolecular hydrogen NH∙∙∙O-Si bonds and CH∙∙∙O=S short contacts. The distribution of electron density in the monomers was determined using quantum chemical calculations of their molecular electrostatic potential (MESP) in an isolated state (in gas) and in a polar medium. The transition from covalent N-Si bonds in crystal compounds and polar medium to non-covalent N∙∙∙Si bonds happened while performing the calculations on the monomer molecules and their dimers in gas. The effect of intermolecular interactions on the strength of the N-Si and N∙∙∙Si bonds in molecules was evaluated through calculations of their complexes with H2O and DMSO.

Discovery of ent-kaurane diterpenoid glucosides as potent analgesics from the leaves of Pieris formosa

To search for structurally novel analgesics from Ericaceae plants, the leaves of Pieris formosa collected at Yichang, Hubei, China, were phytochemically investigated for the first time. A total of fifteen ent-kaurane diterpene glucosides (1–15) including twelve new ones, named forminosides A–L (1–12), were isolated. Their structures were elucidated by comprehensive spectroscopic data analyses, quantum chemical calculations (13C NMR and ECD calculations and DP4+ analysis), and chemical methods. The absolute configures of 1–3, 5–8, 11, and 13 were further determined by single-crystal X-ray diffraction analysis. Forminoside A (1) represents the first 3α-(β-d-glucopyranosyloxy)-11,16-epoxy-ent-kaurane diterpenoid bearing a unique 12-oxa-pentacyclo[9.3.3.01,10.04,9.013,16]heptadecane core. Forminoside J (10) is the first 17-nor-ent-kaurane type diterpenoid from Ericaceae family, while forminoside L (12) represents the first example of 4,5-seco-ent-kaurane diterpenoid glycoside bearing an unusual α-hydroxyl-α,β-unsaturated ketone block. Notably, the structure of mollisside A was revised to 3β-(β-d-glucopyranosyloxy)-16β,17-dihydroxy-ent-kaurane based on the NMR and single-crystal X-ray diffraction data analysis of forminoside C (3). All the isolates 1–15 showed potent analgesic activity in the HOAc-induced writhing test in mice. Among them, compounds 1–3, 5–12, and 15 exhibited significant analgesic effects at a dose of 5.0 mg/kg with the inhibition rates over 50%. Compounds 1, 5, 7, and 9–12 still displayed significant analgesic effects with the inhibition rates exceeding 50% at a lower dose of 1.0 mg/kg. Forminosides J (10) and L (12) still showed significant analgesic potency even at a lower dose of 0.2 mg/kg, comparable to that of the positive control, morphine. This is first report of the analgesic activity of 11,16-epoxy-ent-kaurane diterpenoid. A preliminary structure–activity relationship was explored, providing new clues to design novel analgesics based on the ent-kaurane and related diterpenoids.

Nanostructured spinel ferrites: A comprehensive study on the synthesis, characterization, and magnetic properties of Zn and Mn substituted magnetite nanoparticles produced through the co-precipitation method

Seven cubic spinel ferrite nanoparticles were successfully synthesized through the co-precipitation method. These nanoparticles include Fe3O4, Zn0.4Fe0.62+Fe23+O4, Mn0.4Fe0.62+Fe23+O4, Zn0.6Mn0.4Fe0.42+Fe1.63+O4, Zn0.4Mn0.6Fe0.42+Fe1.63+O4, Zn0.4Mn0.4Fe0.22+Fe23+O4, and Zn0.4Mn0.4Fe0.42+Fe1.83+O4. The Rietveld method was used to analyze X-ray diffraction data, confirming that all samples have a single-phase cubic spinel structure. The presence of zinc and manganese ions in magnetite lattice leads to changes in lattice parameters and crystallite size, resulting in a range of 7–12 nm crystallite sizes. Fourier transform infrared spectroscopy (FT-IR) analysis of nanoparticles reveals two significant adsorption peaks at 560-576 cm−1 and 437-449 cm−1, corresponding to metal ion stretching vibrations at tetrahedral and octahedral sites. The X-ray photoelectron spectroscopy (XPS) analysis revealed the presence of iron, zinc, and manganese in various oxidation states. Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) images showed spherical, agglomerated nanoparticles. The study confirmed the elemental composition and mapping images of prepared samples using energy-dispersive X-ray spectroscopy (EDS). The magnetic properties of the synthesized nanoparticles were meticulously examined utilizing a vibrating sample magnetometer (VSM) at room temperature. A direct correlation is established between the structural alterations induced by Zn2+/Mn2+ and their subsequent effects on magnetic characteristics, specifically through the reallocation of cations and the mechanisms of electron hopping occurring at the B-sites. The structural modifications result in enhanced superparamagnetic behavior, exhibiting saturation magnetization values between 46.01 and 69.38 emu/g. The sustainable characteristics of these materials render them highly viable options for applications in environmental remediation and green technology.

Synthesis, Characterizationand Antibacterial Activity Studyof Para-substituted Derivatives of N -benzyl-3-methylbuten-2-enamides.

In order to deeply explorethe effect of para-substituentson the antibacterial activity ofN-benzyl-3-methylbuten-2-enamidederivatives,we elaborately synthesizedthreesuchpara-substituted derivatives(compounda: N-(4-hydroxybenzyl)-3-methylbut 2-enamide;compoundb:N-(4-isobutoxybenzyl)-3-methylbut-2-enamide;compoundc:N-(4-isopropoxybenzyl)-3-methylbut-2-enamide),of which thestructures were determined by ways of single crystal X-ray diffraction data analysis mainly. The antibacterial performance experiments showed thatcompounds a, band cwere evaluated for their antibacterial (Escherichia coli, Staphylococcus aureus,andEnterobacter aerogenes)activities.Among them, compounds a, band chavean effective antibacterial reagents forE.coliexhibiting MIC values of 0.01,0.01 and0.01g/mL, respectively, but inactive for E. aerogenes.In addition, compounds band chave better activity than compounda against S. aureuswithMIC values of 0.01 and0.02g/mL.These results provide an important basis for further study of the antibacterial properties and structure-activity relationship of these compounds, and are expected to provide valuable reference for the development of new antibacterial drugs.

Structural phase transition from rhombohedral to monoclinic phase and physical properties of (1-x) Bi0.85La0.15FeO3 – (x) Ca0.5Sr0.5TiO3 ceramics prepared by the solid-state route

In the present work, a series of solid solutions were synthesized using the solid-state reaction method for x = 0.0, 0.05, 0.10, and 0.15 in system (1-x)Bi0.85La0.15FeO₃-(x)Ca0.5Sr0.5TiO3 or ((1-x)BLFO-(x)CSTO) ceramics. Structural, optical, dielectric, and ferroelectric properties were studied in detail to investigate the impact of CSTO doping in BFO. Rietveld analysis of X-ray diffraction data of all samples revealed the formation of a single-phase solid solution with a distorted rhombohedral perovskite structure for x = 0.00 and 0.05, characterized by R3c symmetry, a mix of rhombohedral (R3c) and monoclinic (Cc) phases for x = 0.10 (R3c 31 % and Cc 69 %), whereas for x = 0.15 a single-phase solid solution with Cc symmetry was found. UV–visible analysis demonstrated that the optical band gap was increased from 2.11 eV for x = 0.0 to 2.21 eV for x = 0.15 in the visible range, and can be used in photovoltaics applications. The room temperature dielectric properties were measured, and a crucial role of CSTO was revealed in modifying the dielectric properties of BLFO ceramics; the dielectric constant and dielectric loss at 10 kHz change from εr = 82 and tanδ = 0.88 for x = 0.0 to εr = 116 and tanδ = 1.08 for x = 0.15. The leakage current density decreases while increasing the CSTO % from x = 0.0 to 0.15 due to the suppression of oxygen and Bi vacancies, a fact that is further reflected in the ferroelectric properties of CSTO-doped BFO ceramics. Room temperature ferroelectric properties improved with CSTO doping, and Pr was found to be 0.24 μC/cm2, 0.28 μC/cm2, and 0.84 μC/cm2 for x = 0.05, 0.10, and 0.15, respectively.

Application of enaminone ruthenium(II) complexes as catalysts in the transfer hydrogenation of ketones

This study reported the synthesis of two new ligands (1,2) and their Ru(II)-enaminone complexes (3,4). The Ru(II) complexes were obtained from the reaction of the [RuCl2(p-cymene)]2 dimers with the new enaminone derivative ligands (1,2). The use of standard spectroscopy techniques entirely characterized the compounds. Single crystal studies investigated the crystal structure of ligand (1) and complexes (3,4). X-ray diffraction data analysis was used to confirm the enaminone form of 1. Also, 3 and 4 exhibited the classical three-legged piano stool structure with Ru(II) coordinated by the nitrogen and oxygen atoms of 1 and a chloride ligand as the legs and the η6-π-bound p-cymene ligand occupies the seat of the piano stool. The Ru(II) complexes have been studied as catalysts in the transfer hydrogenation of acetophenone and other various ketones in the presence of KOtBu. The catalytic conditions were optimized using different substrate/catalyst and base/catalyst ratios. We found that the complexes show good activities and up to 100 % selectivity. The best turnover frequency (1667 h−1) was found for 3 when using acetophenone as the substrate.

Structural and Electrochemical Characterisation of NBZFO Cobalt-Free Cathode Material for Intermediate-Temperature Solid Oxide Fuel Cells: An Experimental Investigation

Compared to other energy-generating technologies and energy conversion devices, intermediate-temperature solid oxide fuel cells (IT-SOFCs) have gained significant attention from energy experts due to its high energy density, moderate operating temperature (600–800°C), low emissions and reliability. Enhancing the performance of IT-SOFCs requires suitable and excellent cathode materials. Thus, a perovskite-type Nd0.5Ba0.5Zr0.8Fe0.2O3+δ (NBZFO) material was synthesised via traditional solid-state reaction technique and analysed as a potential cathode material for IT-SOFCs. Analysis of X-ray diffraction data (XRD) revealed a single-phase perovskite material that crystallises in cubic space group (pm-3m). The thermal and electrochemical properties were analysed with the aid of thermogravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). NBZFO has an electrical conductivity in air of 80 S cm−1 at 400°C and a polarisation resistance (Rp) of 0.106 Ω cm2 at 800°C. TGA reveals a slight loss in weight of about 0.58%, thereby suggesting a highly stable cathode material for IT-SOFC. Electrochemical investigation shows that NBZFO has good electronic and ionic conductivity and excellent oxygen stichometry. Further studies are required to understand the effects of varying B-site composition of the cathode material.

Analysis of Structures at the Boundary of Contact Melting Al–Mg–Mn and Zn Based Alloys

The processes of contact melting of the AMg6 (Al-6%Mg-1%Mn) alloy with Zn–Cu–Al solder and the model Zn–Al alloy, as well as the structure of the contact fusion zone, are studied. Samples were obtained in two stages. At the first step, the solder was mechanically applied (tinned) to the surface of the AMg6 plates. Аt the second step, the resulting composite samples were subjected to heat treatment with a varied exposure time in the liquid state. According to the data of metallographic and X-ray diffraction analyses, as well as differential scanning calorimetry, it was shown that already at the tinning stage the active interaction between Zn and Al occurs, which leads to the formation of a developed microstructure in the joint zone. The presence of copper in the solder HTS-2000 reduces the melting point of the Zn-Al alloy by 30-40°C and improves the conditions for contact interaction with the grade AMg6 matrix. Active diffusion of zinc ensures the formation of an extensive melting zone during heat treatment, while zinc-rich areas during crystallization contain the Zn5Cu intermetallic phase, which prevents the formation of intermetallic ZnxMgy compounds, which does not lead to embrittlement of the contact zone.

Structural Isomerism in Bimetallic Ag20Cu12 Nanoclusters.

Structural isomers of atomically precise metal nanoclusters are highly sought after for investigating structure-property relationships in nanostructured materials. However, they are extremely rare, particularly those of alloys, primarily due to the challenges in their synthesis and structural characterization. Herein, for the first time, a pair of bimetallic isomeric AgCu nanoclusters has been controllably synthesized and structurally characterized. These two isomers share an identical molecular formula, Ag20Cu12(C≡CR)24 (denoted as Ag20Cu12-1 and Ag20Cu12-2; HC≡CR is 3,5-bis(trifluoromethyl)phenylacetylene). Single-crystal X-ray diffraction data analysis revealed that Ag20Cu12-1 possesses an Ag17Cu4 core composed of two interpenetrating hollow Ag11Cu2 structures. This core is stabilized by four different types of surface motifs: eight -C≡CR, one Cu(C≡CR)2, one Ag3Cu3(C≡CR)6, and two Cu2(C≡CR)4 units. Ag20Cu12-2 features a bitetrahedron Ag14 core, which is stabilized by three Ag2Cu4(C≡CR)8 units. Interestingly, Ag20Cu12-2 undergoes spontaneous transformation to Ag20Cu12-1 in the solution-state. Density functional theory calculations explain the electronic and optical properties and confirm the higher relative stability of Ag20Cu12-1 compared to Ag20Cu12-2. The controlled synthesis and structural isomerism of alloy nanoclusters presented in this work will stimulate and broaden research on nanoscale isomerism.

Green synthesis of copper nanoparticles from Terminalia arjuna (L.) bark extract: Characterization and potential for mercury degradation

The focus of this study is on synthesizing copper nanoparticles through a green approach, utilizing Terminalia arjuna bark extract. The ultra violet (UV) spectral analysis of copper nanoparticles synthesized through environmentally friendly methods revealed distinct absorption peaks at 287 nm, 575 nm, and 898 nm, indicative of significant light absorption. These peaks elucidate the nanoparticles' optical characteristics, shedding light on electronic transitions and surface plasmon resonance phenomena. Fourier transform infrared spectroscopy (FTIR) analysis displayed various peaks, suggesting vibrations associated with copper nanoparticles and functional groups in T. arjuna bark extract. The X-ray diffraction analysis (XRD) data exhibited characteristic peaks corresponding to metallic copper's crystallographic planes, confirming the formation of highly crystalline copper nanoparticles. Atomic force microscopy results depicted surface morphology and particle size distribution. Copper nanoparticles show promise in mercury degradation due to their high surface area and catalytic activity. They interact effectively with mercury ions through adsorption, reduction, and oxidation processes, leading to sequestration or transformation into less toxic forms. Functionalization enhances their affinity towards mercury, while synergies with other nanomaterials boost efficiency. Green synthesized copper nanoparticles offer an eco-friendly solution for effective mercury remediation, promising advancements in sustainable nanotechnological approaches for global environmental sustainability. KEY WORDS: Mercury, Copper, Terminalia arjuna, Remediation Bull. Chem. Soc. Ethiop. 2024, 38(6), 1703-1713. DOI: https://dx.doi.org/10.4314/bcse.v38i6.16

High pressure ferroelectric-like semi-metallic state in Eu-doped BaTiO3.

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits.

The influence of chemical structure spacings on the fluorocopolymers nano-organization

In ternary fluoropolymers Viton GFLT 600S and Viton GFLT 200S, more types of nanoformations with the size of 3–80 nm are found than in double SCF-26 and SCF-32, while their prehistory changes according to the X-ray diffraction analysis data in the region of large angles. This process is more influenced by the chemical structure of the junctions in the macromolecules than by the molecular weight. The complex and unequal character of change of dynamic viscosity of fluoropolymers with temperature increase is caused by multiple phase transitions. It is shown that fluorocarbon rubber SKF-32 does not transition to the viscous-fluid state up to ~190°C in contrast to three fluoropolymers due to intermolecular nanoformations of 5 nm in size, the strength of which is significantly higher than nanoformations of 3–4 nm in the latter. It was found that the rotational mobility of the TEMPO radical is determined not so much by the intermolecular distances in the disordered part of the copolymers as by the flexibility of the passing chains connecting the ordered formations into a single system.

Superconductivity investigation of (Bi, Pb)-2223 added with different nanoferrites and their composites

In this study, the impact of different types of nanoferrites additions of Zn0.5Ni0.5Fe2O4 and Ba0.4Sr0.4Ca0.2Fe12O19 nanoparticles and their nanocomposite of (Zn0.5Ni0.5Fe2O4)0.5 (Ba0.4Sr0.4Ca0.2Fe12O19)0.5 on the structural and normal state resistivity of Bi1.6Pb0.4Sr2Ca2Cu3O10, ((Bi,Pb)-2223) superconducting phase were systematically investigated. The samples were synthesised using high purity oxide powders via a solid-state reaction approach. Based on the Rietveld analysis of x-ray diffraction (XRD) data, the tetragonal structure of (Bi,Pb)-2223 was established to be the predominant phase for all composite samples of the three nano-additions’ contents. However, a little change to the lattice parameters ( a and c ) was obtained. Furthermore, the small amounts (0.04 wt%) of Ba0.4Sr0.4Ca0.2Fe12O19 and (Zn0.5Ni0.5Fe2O4)0.5(Ba0.4Sr0.4Ca0.2Fe12O19)0.5 improved the development of the (Bi,Pb)-2223 phase. The volume fraction of the (Bi,Pb)-2223 phase increased from 86.47% to 88.73% and 88.69%, respectively. Then, it declined to 74.25% and 71.48% upon rising x to 0.40 wt%, respectively, as well as for Zn0.5Ni0.5Fe2O4 nanoparticles up to 0.40 wt%. SEM images verify the host superconducting matrix’s granular structure for all three nanoadditions up to 0.40 wt%. The existence of three nano additions in the host superconductor matrix is verified by employing energy dispersive x-ray (EDX) and x-ray photoelectron spectroscopy (XPS) analysis. The measurements for the resistivity dependency of temperature presented that, as compared to the pure sample (Tc = 108.67 K), the nano-(Zn0.5Ni0.5Fe2O4) x added in the (Bi,Pb)-2223 phase exhibits more negative impact than it is with the other two additions. In contrast, the nano-(Ba0.4Sr0.4Ca0.2Fe12O19) x has the highest value of Tc with a value of 110.95 K at x = 0.04 wt%. Furthermore, the superconducting transition width (∆Tc) improved for all composite samples except for the sample at x = 0.04 wt%, for Ba0.4Sr0.4Ca0.2Fe12O19 and (Zn0.5Ni0.5Fe2O4)0.5 (Ba0.4Sr0.4 Ca0.2Fe12O19)0.5 which showed the sharpest transition width. This suggests that their addition is anticipated to act as artificial pinning centers and strengthen the coupling between the grains in the (Bi,Pb)-2223 ceramic.

Exploring Enhanced Structural and Dielectric Properties in Ag-Doped Sr(NiNb)0.5O3 Perovskite Ceramic for Advanced Energy Storage

The ceramic Sr(NiNb)0.5O3, incorporating silver doping in the A site, was synthesized using a sol–gel route and subjected to comprehensive analysis through various experimental techniques. X-ray diffraction data analysis indicates a rhombohedral crystal structure. Scanning electron microscopy (SEM) examination reveals densely packed grains with minimal surface porosity. A thorough investigation of electrical properties, encompassing dielectric constant, loss tangent, electrical impedance, modulus, conductivity, etc., was conducted across a wide frequency range (103–106 Hz) and temperature range (260–340 K). This analysis provided valuable insights into structure–property relationships and conduction mechanisms. The discussion highlights the significance of interface effects, space charge polarization, and Maxwell–Wagner dielectric relaxation in achieving the material’s high dielectric constant at low frequencies and elevated temperatures. Examination of temperature dependence through Nyquist plots elucidates the contributions of grain behavior to the material’s resistive and capacitive properties. The dielectric permittivity, dissipation of energy, and electrical characteristics like impedance, modulus and conductivity are notably influenced by the frequency of the applied electric field and temperature. Overall, the material exhibits promising potential for industrial applications such as energy storage, given its intriguing properties.

Automated pipeline processing X-ray diffraction data from dynamic compression experiments on the Extreme Conditions Beamline of PETRAIII.

Presented and discussed here is the implementation of a software solution that provides prompt X-ray diffraction data analysis during fast dynamic compression experiments conducted within the dynamic diamond anvil cell technique. It includes efficient data collection, streaming of data and metadata to a high-performance cluster (HPC), fast azimuthal data integration on the cluster, and tools for controlling the data processing steps and visualizing the data using the DIOPTAS software package. This data processing pipeline is invaluable for a great number of studies. The potential of the pipeline is illustrated with two examples of data collected on ammonia-water mixtures and multiphase mineral assemblies under high pressure. The pipeline is designed to be generic in nature and could be readily adapted to provide rapid feedback for many other X-ray diffraction techniques, e.g. large-volume press studies, in situ stress/strain studies, phase transformation studies, chemical reactions studied with high-resolution diffraction etc.

Modulation of Water Vapor Sorption by Pore Engineering in Isostructural Square Lattice Topology Coordination Networks.

We report a crystal-engineering study conducted upon a platform of three mixed-linker square lattice (sql) coordination networks of general formula [Zn(Ria)(bphy)] [bphy = 1,2-bis(pyridin-4-yl)hydrazine, H2Ria = 5-position-substituted isophthalic acid, and R = -Br, -NO2, and -OH; compounds 1-3]. Analysis of single-crystal X-ray diffraction data of 1-2 and the simulated crystal structure of 3 revealed that 1-3 are isomorphous and sustained by bilayers of sql networks linked by hydrogen bonds. Although similar pore shapes and sizes exist in 1-3, distinct isotherm shapes (linear and S shape) and uptakes (2.4, 11.6, and 13.3 wt %, respectively) were observed. Ab initio calculations indicated that the distinct water sorption properties can be attributed to the R groups, which offer a range of hydrophilicity. Calculations indicated that the significantly lower experimental uptake in compound 1 can be attributed to a constricted channel. The calculated water-binding sites provide insights into how adsorbed water molecules bond to the pore walls, with the strongest interactions, water-hydroxyl hydrogen bonding, observed for 3. Overall, this study reveals how pore engineering can result in large variations in water sorption properties in an isomorphous family of rigid porous coordination networks.

Magnetic order induced by magnetic impurities in the Haldane chain compound SrNi2V2O8

Understanding the topological properties of Haldane spin systems offers promising avenues for exploring exotic quantum phases. We investigate the impact of S = 5/2 Mn2+ impurities on the magnetic properties of SrNi2V2O8, a well-known Haldane spin gapped system. Structural characterizations of SrNi2-xMnxV2O8 (x = 0.05, 0.15, 0.30 and 0.60) through Rietveld analyses of X-ray diffraction data confirm the preservation of the I41cd space group for all studied x , along with a preferential insertion of Mn2+ ions into Ni2+ sites. Magnetic susceptibility and magnetization data unveil a magnetic transition occurring in the temperature range of T = 93–99.3 K for x = 0.05–0.60. Dielectric data evince the absence of coupling between magnetic and ferroelectric phases. Notably, the magnetic ordering temperature varies little over a wide range of Mn concentrations, while notable anomalies are observed at x = 0.15. This peculiar behavior suggests that, across low-to-high concentrations, disorder-induced magnetic moments compete with the formation of spin singlets between the nearest Mn2+ impurities, which cancel out the magnetic moments.

Interface engineering and heterometal doping Cu3Se2/WSe2 for efficient charge transfer and nonlinear optical performance

Integrating interface engineering and precious heterometal doping with semiconductors is a feasible pathway to construct efficient charge transfer and improve the nonlinear optical (NLO) performance of materials. Here, we report a bimetallic selenide type-II heterostructure of Cu3Se2/WSe2 (CWS) with a simple one-step magnetron co-sputtering of Cu and WSe2 targets at low argon flow rates. Se first nucleates and precipitates to form nanospheres at low flow rates. Due to the electronegativity of Cu being greater than that of W and Cu prioritizes attachment to the outside of the Se nanospheres and promotes the formation of the nanorods-grown Cu3Se2. A combined analysis of X-ray photoelectron spectroscopy and X-ray diffraction data was used to investigate the minor shift in the W 4 f/Se 2p ratio revealing that electrons shifted from Cu3Se2 to WSe2. The diffraction peaks of CWS and the valence electronic structure of Cu1+/Cu2+ confirmed the implantation of Cu3Se2 nanorods on WSe2. The NLO properties of CWS composite films were modulated by varying the power of Cu. More importantly, the nonlinear absorption coefficient of the CWS composite films formed after Cu3Se2 promotion is much better than that of other unmodified pure WSe2 films. The photogenerated carrier dynamics of CWS composite films were investigated by femtosecond transient absorption spectroscopy, and density functional theory calculations show that CWS composite films inhibit efficient electron transfer photogenerated carrier complexation. This work proposes a few strategies for designing heterogeneous structures with interface engineering and precious metal doping to promote adjustable electron transfer dynamics and achieve high NLO conversion efficiency.

Seeing the Unseen: The Structural Influence of the Lone Pair Electrons in PbWO4.

Pair distribution function (PDF) analysis of the scheelite-type material PbWO4 reveals previously unidentified short-range structural distortions in the PbO8 polyhedra and WO4 tetrahedra not observed in the similarly structured CaWO4. These local distortions are a result of the structural influence of the Pb2+ 6s2 lone pair electrons. These are not evident from the Rietveld analysis of synchrotron X-ray or neutron powder diffraction data, nor do they strongly influence the X-ray PDF (XPDF). This illustrates the importance of neutron PDF (NPDF) in the study of such materials. First-principles density function theory (DFT) calculations show that the Pb2+ 6s2 electrons are hybridized with the O2- 2p electrons near the Fermi level. The presence of local-scale distortions has previously been neglected in studies of structure-functionality relationships in PbWO4 and other scheelite-structured photocatalytic materials, including BiVO4, and this observation opens new avenues for their optimization.