Pair Distribution Function Analysis Research Articles

Ultralow Thermal Conductivity in Vacancy-Ordered Halide Perovskite Cs3Bi2Br9 with Strong Anharmonicity and Wave-Like Tunneling of Low-Energy Phonons.

Halide perovskites are of great interest due to their exceptional optical and optoelectronic properties. However, thermal conductivity of many halide perovskites remains unexplored. In this study, an ultralow lattice thermal conductivity κL (0.24W m-1 K-1 at 300 K) is reported and its weak temperature dependence (≈T-0.27) in an all-inorganic vacancy-ordered halide perovskite, Cs3Bi2Br9. The intrinsically ultralow κL can be attributed to the soft low-lying phonon modes with strong anharmonicity, which have been revealed by combining experimental heat capacity and Raman spectroscopy measurements, and first-principles calculations. It is shown that the highly anharmonic phonons originate from the Bi 6s2 lone pair expression with antibonding states of Bi 6s and Br 4p orbitals driven by the dynamic BiBr6 octahedral distortion. Theoretical calculations reveal that these low-energy phonons are mostly contributed by large Br motions induced dynamic distortion of BiBr6 octahedra and large Cs rattling motions, verified by the synchrotron X-ray pair distribution function analysis. In addition, the weak temperature dependence of κL can be traced to the wave-like tunneling of phonons, induced by the low-lying phonon modes. This work reveals the strong anharmonicity and wave-like tunneling of low-energy phonons for designing efficient vacancy-ordered halide perovskites with intrinsically low κL.

Operando pair distribution function analysis of nanocrystalline functional materials: the case of TiO2-bronze nanocrystals in Li-ion battery electrodes

Structural modelling of operando pair distribution function (PDF) data of complex functional materials can be highly challenging. To aid the understanding of complex operando PDF data, this article demonstrates a toolbox for PDF analysis. The tools include denoising using principal component analysis together with the structureMining, similarityMapping and nmfMapping apps available through the online service `PDF in the cloud' (PDFitc, https://pdfitc.org/). The toolbox is used for both ex situ and operando PDF data for 3 nm TiO2-bronze nanocrystals, which function as the active electrode material in a Li-ion battery. The tools enable structural modelling of the ex situ and operando PDF data, revealing two pristine TiO2 phases (bronze and anatase) and two lithiated Li x TiO2 phases (lithiated versions of bronze and anatase), and the phase evolution during galvanostatic cycling is characterized.

Comprehensive Investigation of the Crystal Structure of Cation-Disordered Li3VO4 as a High-Rate Anode Material: Unveiling the Dichotomy between Order and Disorder.

This study investigates mechanochemical synthesis and cation-disordering mechanism of wurtzite-type Li3VO4 (LVO), highlighting its promise as a high-performance anode material for lithium-ion batteries and hybrid supercapacitors. Mechanochemical treatment of pristine LVO using a high-energy ball mill results in a "pure cation-disordered" LVO phase, allowing for meticulous analysis of cation arrangement. The X-ray and neutron diffraction study demonstrates progressive loss of order in LVO crystal with increasing milling duration. High-resolution transmission electron microscopy reveals disrupted lattice fringes, indicating cationic misalignment. Pair-distribution function analysis confirms loss of cation arrangements and the presence of short-range order. Combination of these multiple analytical techniques achieves a comprehensive understanding of cation regularity and clearly demonstrates order/disorder dichotomy in cation-disordered materials, ranging from short (<8 Å) to middle-long range (8-30 Å), using an integrated superstructure model of the cation-disordered LVO crystals. Electrochemical testing reveals that mechanochemically treated LVO exhibits superior rate capability, with a 70% capacity retention at a high current density of 50C-rate. Lithium diffusion coefficient measurements demonstrate enhanced lithium-ion mobility in the mechanochemically treated LVO, attributed to cation-disordering effect. These findings provide valuable insights into mechanochemical cation-disordering in LVO, presenting its potential as an efficient anode material for lithium-ion-based electrochemical energy storage.

Insights into the nucleation and growth of BiOCl nanoparticles by in situ X-ray pair distribution function analysis and in situ liquid cell TEM.

The synthesis of bismuth oxyhalides as defined nanostructures is hindered by their fast nucleation and growth in aqueous solutions. Using our recently developed single-source precursor, the formation of bismuth oxychloride in such solutions can be slowed significantly. As reported herein, this advance enables BiOCl formation to be investigated by in situ X-ray total scattering and in situ liquid cell transmission electron microscopy. In situ pair distribution function analysis of X-ray total scattering data reveals the local order of atomic structures throughout the synthesis, while in situ liquid cell transmission electron microscopy allows for tracking the growth of individual nanoparticles. Through this work, the precursor complex is shown to give rise to BiOCl upon heating in solution without the observation of structurally distinct intermediates. The emerging nanoparticles have a widened interlayer spacing, which moderately decreases as the particles grow. Mechanistic insights into the formation of bismuth oxyhalide nanoparticles, including the absence of distinct intermediates within the available time resolution, will help facilitate future design of controlled BiOX nanostructures.

Different or the same? exploring the physicochemical properties and molecular mobility of celecoxib amorphous forms

The influence of different preparation methods on the physicochemical properties of amorphous solid forms have gained considerable attention, especially with recent publications on pharmaceutical polyamorphism. In the present study, we have investigated the possible occurrence of polyamorphism in the drug celecoxib (CEL) by investigating the thermal behavior, morphology, structure, molecular mobility and physical stability of amorphous CEL obtained by quench-cooling (QC), ball milling (BM) and spray drying (SD). Similar glass transition temperatures but different recrystallization behaviors were observed for CEL-QC, CEL-BM and CEL-SD using modulated differential scanning calorimetry analysis. A correlation between the different recrystallization behaviors of the three CEL amorphous forms and the respective distinct powder morphologies, was also found. Molecular dynamics simulations however, reveal that CEL presents similar molecular conformational distributions when subjected to QC and SD. Moreover, the obtained molecular conformational distributions of CEL are different from the ones found in its crystal structure and also from the ones found in the lowest-energy structure obtained by quantum mechanical calculations. The type and strength of CEL hydrogen bond interactions found in CEL-QC and CEL-SD systems are almost identical, though different from the ones presented in the crystal structure. Pair distribution function analyses and isothermal microcalorimetry show similar local structures and structural relaxation times, respectively, for CEL-QC, CEL-BM and CEL-SD. The present work shows that not only similar physicochemical properties (glass transition temperature, and structural relaxation time), but also similar molecular conformational distributions were observed for all prepared CEL amorphous systems. Hence, despite their different recrystallization behaviors, the three amorphous forms of CEL did not show any signs of polyamorphism.

3D Lead-Organoselenide-Halide Perovskites and their Mixed-Chalcogenide and Mixed-Halide Alloys.

We incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se-), which occupies both the X- and A+ sites in the prototypical ABX3 perovskite. The new organoselenide-halide perovskites: (SeCYS)PbX2 (X = Cl, Br) expand upon the recently discovered organosulfide-halide perovskites. Single-crystal X-ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide-halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid-state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable bandgap decrease. Optical absorbance measurements indeed show bandgaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X = Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the bandgap from 1.86 to 2.31 eV-straddling the ideal range for tandem solar cells or visible-light photocatalysis. The comprehensive description of the average and local structures, and how they can fine-tune the bandgap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid-state and organo-main-group chemistry.

3D Lead-Organoselenide-Halide Perovskites and their Mixed-Chalcogenide and Mixed-Halide Alloys.

We incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se-), which occupies both the X- and A+ sites in the prototypical ABX3 perovskite. The new organoselenide-halide perovskites: (SeCYS)PbX2 (X = Cl, Br) expand upon the recently discovered organosulfide-halide perovskites. Single-crystal X-ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide-halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid-state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable bandgap decrease. Optical absorbance measurements indeed show bandgaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X = Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the bandgap from 1.86 to 2.31 eV-straddling the ideal range for tandem solar cells or visible-light photocatalysis. The comprehensive description of the average and local structures, and how they can fine-tune the bandgap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid-state and organo-main-group chemistry.

3D Lead‐Organoselenide‐Halide Perovskites and their Mixed‐Chalcogenide and Mixed‐Halide Alloys

We incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se−), which occupies both the X− and A+ sites in the prototypical ABX3 perovskite. The new organoselenide‐halide perovskites: (SeCYS)PbX2 (X = Cl, Br) expand upon the recently discovered organosulfide‐halide perovskites. Single‐crystal X‐ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide‐halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid‐state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable bandgap decrease. Optical absorbance measurements indeed show bandgaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X = Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the bandgap from 1.86 to 2.31 eV—straddling the ideal range for tandem solar cells or visible‐light photocatalysis. The comprehensive description of the average and local structures, and how they can fine‐tune the bandgap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid‐state and organo‐main‐group chemistry.

3D Lead‐Organoselenide‐Halide Perovskites and their Mixed‐Chalcogenide and Mixed‐Halide Alloys

We incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se−), which occupies both the X− and A+ sites in the prototypical ABX3 perovskite. The new organoselenide‐halide perovskites: (SeCYS)PbX2 (X = Cl, Br) expand upon the recently discovered organosulfide‐halide perovskites. Single‐crystal X‐ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide‐halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid‐state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable bandgap decrease. Optical absorbance measurements indeed show bandgaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X = Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the bandgap from 1.86 to 2.31 eV—straddling the ideal range for tandem solar cells or visible‐light photocatalysis. The comprehensive description of the average and local structures, and how they can fine‐tune the bandgap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid‐state and organo‐main‐group chemistry.

Improving Hydrogen Release From Oxygen‐Functionalized LOHC Molecules by Ru Addition to Pt/C Catalysts

AbstractBimetallic PtRu/C catalysts have been prepared by depositing Ru onto a commercial Pt/C catalyst and subsequent thermal annealing. Different Pt : Ru ratios of 1 : 1, 2 : 1, 4 : 1, 8 : 1, and 16 : 1 have been investigated with annealing temperatures of 350 and 500 °C. Using X‐ray diffraction (XRD), synchrotron powder X‐ray diffraction (SPXRD) combined with pair distribution function (PDF) analysis and scanning transmission electron microscopy with energy dispersive X‐ray spectrum imaging (STEM‐EDXS), we show that diffusion of Ru into the fcc crystal structure of the Pt nanoparticles takes place during thermal annealing. Partial segregation and the formation of Pt nanoclusters on the bimetallic surface was observed depending on the Pt : Ru ratio. The annealing process does not only cause a high Pt dispersion but also affects the electronic structure of the Pt surface by broadening the d‐band thus facilitating the product's desorption from the surface of the bimetallic particle. These beneficial effects have been exemplified for the catalytic dehydrogenation of dicyclohexylmethanol, a promising hydrogen carrier compound with 7.2 wt% hydrogen capacity. The most active catalyst material among the tested supported alloys and monometallic reference materials was Pt4Ru1/C after annealing at 500 °C, which increased the hydrogen release productivity by 65 % compared to the unmodified Pt/C catalyst.

Multiscale investigation on the formation path of the apatite phase in bioactive glasses

Mesoporous bioactive glasses (MBGs) have been reported as promising biomaterials to stimulate and promote the growth of bones. When exposed to Simulated Body Fluid (SBF), MBGs develop an apatite phase called carbonate hydroxyapatite (H(C)A) on their surfaces that closely mimics the mineral phase of bones. In order to gain deeper insights into the key stages of the surface reactions of two different types of MBGs (58S and 70S30C) soaked in SBF, we have used high energy total X-ray scattering coupled to Pair Distribution Function (PDF) analysis, along with Raman spectroscopy and scanning electron microscopy. This type of coupled analytical approach can ultimately help to unravel the details of the reaction kinetics in the complex calcium phosphate environment around the BGs surfaces. The data obtained in our in-vitro study point to the formation of other intermediate phases like amorphous calcium phosphate (ACP) and calcite (CC), that transform after a specific time into H(C)A depending on the composition of the MBGs, their surface properties and their interaction times with SBF.

Tracking copper nanofiller evolution in polysiloxane during processing into SiOC ceramic

Polymer-derived ceramics (PDCs) remain at the forefront of research for a variety of applications including ultra-high-temperature ceramics, energy storage and functional coatings. Despite their wide use, questions remain about the complex structural transition from polymer to ceramic and how local structure influences the final microstructure and resulting properties. This is further complicated when nanofillers are introduced to tailor structural and functional properties, as nanoparticle surfaces can interact with the matrix and influence the resulting structure. The inclusion of crystalline nanofiller produces a mixed crystalline–amorphous composite, which poses characterization challenges. With this study, we aim to address these challenges with a local-scale structural study that probes changes in a polysiloxane matrix with incorporated copper nanofiller. Composites were processed at three unique temperatures to capture mixing, pyrolysis and initial crystallization stages for the pre-ceramic polymer. We observed the evolution of the nanofiller with electron microscopy and applied synchrotron X-ray diffraction with differential pair distribution function (d-PDF) analysis to monitor changes in the matrix's local structure and interactions with the nanofiller. The application of the d-PDF to PDC materials is novel and informs future studies to understand interfacial interactions between nanofiller and matrix throughout PDC processing.

Intercalated Water Drives Anomalous Thermal Expansion in the Tetragonal Zircon Structured Bismuth Vanadate BiVO4 Photocatalyst.

The thermal transformation of zircon to scheelite in BiVO4 was studied by in-situ Synchrotron X-ray diffraction and TGA/FTIR analysis. Upon heating, the tetragonal zircon polymorph of BiVO4 (tz-BiVO4) transitioned to the tetragonal scheelite (ts-)polymorph between 693-773 K, then to monoclinic fergusonite (mf) polymorph upon cooling. An anomaly in thermal expansion was observed between 400-500 K, associated with loss of H2O/NH4+. Heating tz-BiVO4 resulted in contraction of the V-O bond distance and VO4 polyhedra volume due to rotation of the VO4. Attempts to study this by neutron diffraction failed due to the large incoherent scatter from the hydrogenous species. Efforts to remove these species while maintaining the tz-BiVO4 structure were unsuccessful, suggesting they play a role in stabilizing the zircon polymorph. The local structure of both mf-BiVO4 and tz-BiVO4 were investigated by X-ray Pair Distribution Function analysis.

Local structural modelling and local pair distribution function analysis for Zr–Pt metallic glass

In disordered glass structures, the structural modelling and analyses based on local experimental data are not yet established. Here we investigate the icosahedral short-range order (SRO) in a Zr–Pt metallic glass using local structural modelling, which is a reverse Monte Carlo simulation dedicated to two-dimensional angstrom-beam electron diffraction (ABED) patterns, and local pair distribution function (PDF) analysis. The local structural modelling invariably leads to the icosahedral SRO atomic configurations that are similarly distorted by starting from some different initial configurations. Furthermore, the SRO configurations with 11–13 coordination numbers reproduce almost identical ABED patterns, indicating that these SRO structures are similar to each other. Further local PDF analysis explicitly indicates the presence of the wide distribution of atomic bond distances, which is comparable to the global PDF profile, even at the SRO level. The SRO models based on the conventional MD simulation can be strengthened by comparison with those obtained by the present local structural modelling and local PDF analysis based on the ABED data.

Investigation of the Structure of Highly Dispersed NiO–SiO2 Catalyst Features Using X-Ray Analysis of the Atomic Pair Distribution Function

Investigation of the Structure of Highly Dispersed NiO–SiO2 Catalyst Features Using X-Ray Analysis of the Atomic Pair Distribution Function

Structural Evolution and Photoluminescence Quenching across the FASnI3-xBrx (x = 0-3) Perovskites.

One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI3-xBrx (x = 0-3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0-2.9; x = 2.9-3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s2 lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0-2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA+ cation. In contrast to the FAPbI3-xBrx series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. Our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr6] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.

Uncovering Atomic-scale Dynamics in Solid Catalysts via X-ray-based Methods.

Deciphering the structural intricacies of catalysts is essential to advance their atomic-scale engineering. Solid catalysts are complex, with structural features spanning multiple length scales and involving dynamics, which possess challenges in understanding structure-performance relationships. However, advanced operando X-ray characterization techniques, including X-ray absorption spectroscopy (XAS), diffraction (XRD), and pair distribution function analysis (PDF) allow elucidation of structural features under working conditions, discovering transitions from supported nanocrystals to dispersed sites, from solid solutions to supported nanoparticles, or structural changes at the local level. In this mini-review, we discuss case studies exploring the structure of catalysts over different lengths and time scales under different applications, such as CO2 hydrogenation to methanol or the dry reforming of methane, using a combination of operando XAS, XRD and PDF.

Design and Application of a Gas Diffusion Electrode (GDE) Cell for Operando and In Situ Studies.

Presented here is an electrochemical three-electrode Gas Diffusion Electrode (GDE) cell tailored for operandoand in situ investigations of electrocatalytic processes, with a particular focus on X-ray scattering studies. The optimized cell is engineered to accommodate the minimal sample-detector distances requisite for comprehensive X-ray total scattering investigations. An in-depth understanding of catalytic processes requires their study under 'working' conditions. Configured as a flow-cell, the setup therefore enables the examination of electrocatalysts under high current densities and associated gas evolution phenomena, particularly pertinent for reactions like the oxygen evolution reaction (OER). Notably, its transparency simplifies cell alignment, troubleshooting, and facilitates scans through the catalyst layer, crucial for background corrections. Demonstrating its versatility, we showcase its utility through Small Angle X-ray Scattering (SAXS), X-ray Diffraction (XRD), and X-ray Pair Distribution Function (PDF) analyses of total scattering data.

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.

The Optimization of Pair Distribution Functions for the Evaluation of the Degree of Disorder and Physical Stability in Amorphous Solids.

The amorphous form of poorly soluble drugs is physically unstable and prone to crystallization, resulting in decreased solubility and bioavailability. However, the conventional accelerated stability test for amorphous drugs is time-consuming and inaccurate. Therefore, there is an urgent need to develop rapid and accurate stability assessment technology. This study used the antitumor drug nilotinib free base as a model drug. The degree of disorder and physical stability in the amorphous form was assessed by applying the pair distribution function (PDF) and principal component analysis (PCA) methods based on powder X-ray diffraction (PXRD) data. Specifically, the assessment conditions, such as the PDF interatomic distance range, PXRD detector type, and PXRD diffraction angle range were also optimized. The results showed that more reliable PCA data could be obtained when the PDF interatomic distance range was 0-15 Å. When the PXRD detector was a semiconductor-type detector, the PDF data obtained were more accurate than other detectors. When the PXRD diffraction angle range was 5-40°, the intermolecular arrangement of the amorphous drugs could be accurately predicted. Finally, the accelerated stability test also showed that under the above-optimized conditions, this method could accurately and rapidly assess the degree of disorder and physical stability in the amorphous form of drugs, which has obvious advantages compared with the accelerated stability test.