Ultrafast Symmetry Control in Photoexcited Quantum Dots.

Symmetry control is essential for realizing unconventional properties, such as ferroelectricity, nonlinear optical responses, and complex topological order, thus it holds promise for the design of emerging quantum and photonic systems. Nevertheless, fast and reversible control of symmetry in materials remains a challenge, especially for nanoscale systems. Here, reversible symmetry changes are unveiled in colloidal lead chalcogenide quantum dots on picosecond timescales.

Structural Disorder of a Layered Lithium Manganese Oxide Cathode Paving a Reversible Phase Transition Route toward Its Theoretical Capacity.

Layered lithium manganese oxides suffer from irreversible phase transitions induced by Mn migration and/or dissolution associated with the Jahn-Teller effect (JTE) of Mn, leading to inevitable capacity fading during cycling. The popular doping strategy of oxidizing Mn to Mn to relieve the JTE cannot completely eliminate the detrimental structural collapse from the cooperative JTE. Therefore, they are considered to be impractical for commercial use as cathode materials.

Correlated Anion Disorder in Heteroanionic Cubic TiOF.

Resolving anion configurations in heteroanionic materials is crucial for understanding and controlling their properties. For anion-disordered oxyfluorides, conventional Bragg diffraction cannot fully resolve the anionic structure, necessitating alternative structure determination methods. We have investigated the anionic structure of anion-disordered cubic (ReO-type) TiOF using X-ray pair distribution function (PDF), F MAS NMR analysis, density functional theory (DFT), cluster expansion modeling, and genetic-algorithm structure prediction.

Observation of a Picosecond Light-Induced Spin Transition in Polymeric Nanorods.

Spin transition (ST) materials are attractive for developing photoswitchable devices, but their slow material transformations limit device applications. Size reduction could enable faster switching, but the photoinduced dynamics at the nanoscale remains poorly understood. Here, we report a femtosecond optical pump multimodal X-ray probe study of polymeric nanorods.

Goethite and Hematite Nucleation and Growth from Ferrihydrite: Effects of Oxyanion Surface Complexes.

The presence of oxyanions, such as nitrate (NO) and phosphate (PO), regulates the nucleation and growth of goethite (Gt) and hematite (Hm) during the transformation of ferrihydrite (Fh). Our previous studies showed that oxyanion surface complexes control the rate and pathway of Fh transformation to Gt and Hm. However, how oxyanion surface complexes control the mechanism of Gt and Hm nucleation and growth during the Fh transformation is still unclear.

Orientational analysis of atomic pair correlations in nanocrystalline indium oxide thin films.

The application of grazing-incidence total X-ray scattering (GITXS) for pair distribution function (PDF) analysis using >50 keV X-rays from synchrotron light sources has created new opportunities for structural characterization of supported thin films with high resolution. Compared with grazing-incidence wide-angle X-ray scattering, which is only useful for highly ordered materials, GITXS/PDFs expand such analysis to largely disordered or nanostructured materials by examining the atomic pair correlations dependent on the direction relative to the surface of the supporting substrate. A characterization of nanocrystalline InO-derived thin films is presented here with in-plane-isotropic and out-of-plane-anisotropic orientational ordering of the atomic structure, each synthesized using different techniques.

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF.

Introducing compositional or structural disorder within crystalline solid electrolytes is a common strategy for increasing their ionic conductivity. (M,Sn)F fluorites have previously been proposed to exhibit two forms of disorder within their cationic host frameworks: occupational disorder from randomly distributed M and Sn cations and orientational disorder from Sn(II) stereoactive lone pairs. Here, we characterize the structure and fluoride-ion dynamics of cubic BaSnF, using a combination of experimental and computational techniques.

In situ X-ray area detector flat-field correction at an operating photon energy without flat illumination. Corrigendum.

The name of an author in the article by Weng et al. (2023) [J. Synchrotron Rad.

In situ X-ray area detector flat-field correction at an operating photon energy without flat illumination.

Flat-field calibration of X-ray area detectors is a challenge due to the inability to generate an X-ray flat-field at the selected photon energy the beamline operates at, which has a strong influence on the measurement behavior of the detector. A method is presented in which a simulated flat-field correction is calculated without flat-field measurements. Instead, a series of quick scattering measurements from an amorphous scatterer is used to calculate a flat-field response.

Extended q-Range X-Ray Scattering Reveals High-Resolution Structural Details of Biomacromolecules in Aqueous Solutions.

We communicate a feasibility study for high-resolution structural characterization of biomacromolecules in aqueous solution from X-ray scattering experiments measured over a range of scattering vectors (q) that is approximately two orders of magnitude wider than used previously for such systems. Scattering data with such an extended q-range enables the recovery of the underlying real-space atomic pair distribution function, which facilitates structure determination. We demonstrate the potential of this method for biomacromolecules using several types of cyclodextrins (CD) as model systems.

Oxyanion Surface Complexes Control the Kinetics and Pathway of Ferrihydrite Transformation to Goethite and Hematite.

The rate and pathway of ferrihydrite (Fh) transformation at oxic conditions to more stable products is controlled largely by temperature, pH, and the presence of other ions in the system such as nitrate (NO), sulfate (SO), and arsenate (AsO). Although the mechanism of Fh transformation and oxyanion complexation have been separately studied, the effect of surface complex type and strength on the rate and pathway remains only partly understood. We have developed a kinetic model that describes the effects of surface complex type and strength on Fh transformation to goethite (Gt) and hematite (Hm).

Spontaneous Strain Buffer Enables Superior Cycling Stability in Single-Crystal Nickel-Rich NCM Cathode.

The capacity degredation in layered Ni-rich LiNiCoMnO ( ≥ 0.8) cathode largely originated from drastic surface reactions and intergranular cracks in polycrystalline particles. Herein, we report a highly stable single-crystal LiNiCoMnO cathode material, which can deliver a high specific capacity (∼209 mAh g at 0.

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides.

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure.

Intercalation-exfoliation processes during ionic exchange reactions from sodium lepidocrocite-type titanate toward a proton-based trititanate structure.

Topochemical reactions involving ionic exchange have been used to assess a large number of metastable compositions, particularly in layered metal oxides. This method encompasses complex reactions that are poorly explored, yet are of prime importance to understand and control the materials' properties. In this work, we embark on investigating the reactions involved during the ionic exchange between a layered Na-titanate (lepidocrocite-type structure) and an acidic solution (HCl), leading to a protonic (H3O+) titanate (trititanate structure).

Resolving the Atomic Structure of Sequential Infiltration Synthesis Derived Inorganic Clusters.

Sequential infiltration synthesis (SIS) is a route to the precision deposition of inorganic solids in analogy to atomic layer deposition but occurs within (vs upon) a soft material template. SIS has enabled exquisite nanoscale morphological complexity in various oxides through selective nucleation in block copolymers templates. However, the earliest stages of SIS growth remain unresolved, including the atomic structure of nuclei and the evolution of local coordination environments, before and after polymer template removal.

Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte NaPS.

Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor NaPS are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg and pair distribution function), spectroscopy (impedance, Raman, NMR and INS), and simulations aimed at elucidating the synthesis-property relationships in NaPS.

Thermal Stability and Decomposition Products of P-Doped Ferrihydrite.

This work aimed to determine the effect of various amounts of P admixtures in synthetic ferrihydrite on its thermal stability, transformation processes, and the properties of the products, at a broad range of temperatures up to 1000 °C. A detailed study was conducted using a series of synthetic ferrihydrites FeHO·4HO doped with phosphates at P/Fe molar ratios of 0.2, 0.

Atomic Insights into Aluminium-Ion Insertion in Defective Anatase for Batteries.

Aluminium batteries constitute a safe and sustainable high-energy-density electrochemical energy-storage solution. Viable Al-ion batteries require suitable electrode materials that can readily intercalate high-charge Al ions. Here, we investigate the Al intercalation chemistry of anatase TiO and how chemical modifications influence the accommodation of Al ions.

Redox Cycling Driven Transformation of Layered Manganese Oxides to Tunnel Structures.

Mn oxides are among the most ubiquitous minerals on Earth and play critical roles in numerous elemental cycles in biotic/abiotic loops as the key redox center. Yet, it has long puzzled geochemists why the laboratory synthesis of todorokite, a tunnel-structured Mn oxide, is extremely difficult while it is the dominant form over other tunneled phases in low-temperature natural environments. This study employs a novel electrochemical method to mimic the cyclic redox reactions occurring over long geological time scales in an accelerated manner.

Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides.

Cation ordering/disordering in spinel oxides plays an essential role in the rich physical and chemical properties which are hallmarks of the structural archetype. A variety of cation-ordering motifs have been reported for spinel oxides with multiple cations residing on the octahedral site (or B-site). This has attracted tremendous attention from both experimental and theoretical communities in the last few decades.

A new method for in situ structural investigations of nano-sized amorphous and crystalline materials using mixed-flow reactors.

Structural investigations of amorphous and nanocrystalline phases forming in solution are historically challenging. Few methods are capable of in situ atomic structural analysis and rigorous control of the system. A mixed-flow reactor (MFR) is used for total X-ray scattering experiments to examine the short- and long-range structure of phases in situ with pair distribution function (PDF) analysis.

Red-Shifted Absorptions of Cation-Defective and Surface-Functionalized Anatase with Enhanced Photoelectrochemical Properties.

Manipulating the atomic structure of semiconductors is a fine way to tune their properties. The rationalization of their modified properties is, however, particularly challenging as defects locally disrupt the long-range structural ordering, and a deeper effort is required to fully describe their structure. In this work, we investigated the photoelectrochemical properties of an anatase-type structure featuring a high content of titanium vacancies stabilized by dual-oxide substitution by fluoride and hydroxide anions.

Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length.

The nature of the interface between the solute and the solvent in a colloidal solution has attracted attention for a long time. For example, the surface of colloidal nanocrystals (NCs) is specially designed to impart colloidal stability in a variety of polar and nonpolar solvents. This work focuses on a special type of colloids where the solvent is a molten inorganic salt or organic ionic liquid.