Japan Synchrotron Radiation Research Institute

In situ x-ray diffraction measurements of MgSiO3 were performed at high pressure and temperature similar to the conditions at Earth's core-mantle boundary. Results demonstrate that MgSiO3 perovskite transforms to a new high-pressure form with stacked SiO6-octahedral sheet structure above 125 gigapascals and 2500 kelvin (2700-kilometer depth near the base of the mantle) with an increase in density of 1.0 to 1.2%. The origin of the D" seismic discontinuity may be attributed to this post-perovskite phase transition. The new phase may have large elastic anisotropy and develop preferred orientation with platy crystal shape in the shear flow that can cause strong seismic anisotropy below the D" discontinuity.

A π-conjugated nanosheet comprising planar nickel bis(dithiolene) complexes was synthesized by a bottom-up method. A liquid-liquid interfacial reaction using benzenehexathiol in the organic phase and nickel(II) acetate in the aqueous phase produced a semiconducting bulk material with a thickness of several micrometers. Powder X-ray diffraction analysis revealed that the crystalline portion of the bulk material comprised a staggered stack of nanosheets. A single-layer nanosheet was successfully realized using a gas-liquid interfacial reaction. Atomic force microscopy and scanning tunneling microscopy confirmed that the π-conjugated nanosheet was single-layered. Modulation of the oxidation state of the nanosheet was possible using chemical redox reactions.

Abstract Dry reforming of methane (DRM) is an attractive route to utilize CO 2 as a chemical feedstock with which to convert CH 4 into valuable syngas and simultaneously mitigate both greenhouse gases. Ni-based DRM catalysts are promising due to their high activity and low cost, but suffer from poor stability due to coke formation which has hindered their commercialization. Herein, we report that atomically dispersed Ni single atoms, stabilized by interaction with Ce-doped hydroxyapatite, are highly active and coke-resistant catalytic sites for DRM. Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH 4 , thus avoiding methane deep decomposition into carbon. This discovery offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.

Abstract Surface-supported isolated atoms in single-atom catalysts (SACs) are usually stabilized by diverse defects. The fabrication of high-metal-loading and thermally stable SACs remains a formidable challenge due to the difficulty of creating high densities of underpinning stable defects. Here we report that isolated Pt atoms can be stabilized through a strong covalent metal-support interaction (CMSI) that is not associated with support defects, yielding a high-loading and thermally stable SAC by trapping either the already deposited Pt atoms or the PtO 2 units vaporized from nanoparticles during high-temperature calcination. Experimental and computational modeling studies reveal that iron oxide reducibility is crucial to anchor isolated Pt atoms. The resulting high concentrations of single atoms enable specific activities far exceeding those of conventional nanoparticle catalysts. This non defect-stabilization strategy can be extended to non-reducible supports by simply doping with iron oxide, thus paving a new way for constructing high-loading SACs for diverse industrially important catalytic reactions.

$\ensuremath{\alpha}\text{-FeSe}$ with the PbO structure is a key member of the family of high-${T}_{c}$ iron pnictide and chalcogenide superconductors, as while it possesses the basic layered structural motif of edge-sharing distorted ${\text{FeSe}}_{4}$ tetrahedra, it lacks interleaved ion spacers or charge-reservoir layers. We find that the application of hydrostatic pressure first rapidly increases ${T}_{c}$ which attains a broad maximum of 37 K at $\ensuremath{\sim}7\text{ }\text{GPa}$ before decreasing to 6 K upon further compression to $\ensuremath{\sim}14\text{ }\text{GPa}$. Complementary synchrotron x-ray diffraction at 16 K was used to measure the low-temperature isothermal compressibility of $\ensuremath{\alpha}\text{-FeSe}$, revealing an extremely soft solid with a bulk modulus, ${K}_{0}=30.7(1.1)\text{ }\text{GPa}$ and strong bonding anisotropy between interlayer and intralayer directions that transforms to the more densely packed $\ensuremath{\beta}$ polymorph above $\ensuremath{\sim}9\text{ }\text{GPa}$. The nonmonotonic ${T}_{c}(P)$ behavior of FeSe coincides with drastic anomalies in the pressure evolution of the interlayer spacing, pointing to the key role of this structural feature in modulating the electronic properties.

The Hayabusa spacecraft successfully recovered dust particles from the surface of near-Earth asteroid 25143 Itokawa. Synchrotron-radiation x-ray diffraction and transmission and scanning electron microscope analyses indicate that the mineralogy and mineral chemistry of the Itokawa dust particles are identical to those of thermally metamorphosed LL chondrites, consistent with spectroscopic observations made from Earth and by the Hayabusa spacecraft. Our results directly demonstrate that ordinary chondrites, the most abundant meteorites found on Earth, come from S-type asteroids. Mineral chemistry indicates that the majority of regolith surface particles suffered long-term thermal annealing and subsequent impact shock, suggesting that Itokawa is an asteroid made of reassembled pieces of the interior portions of a once larger asteroid.

Flexible porous coordination polymers change their structure in response to molecular incorporation but recover their original configuration after the guest has been removed. We demonstrated that the crystal downsizing of twofold interpenetrated frameworks of [Cu(2)(dicarboxylate)(2)(amine)](n) regulates the structural flexibility and induces a shape-memory effect in the coordination frameworks. In addition to the two structures that contribute to the sorption process (that is, a nonporous closed phase and a guest-included open phase), we isolated an unusual, metastable open dried phase when downsizing the crystals to the mesoscale, and the closed phase was recovered by thermal treatment. Crystal downsizing suppressed the structural mobility and stabilized the open dried phase. The successful isolation of two interconvertible empty phases, the closed phase and the open dried phase, provided switchable sorption properties with or without gate-opening behavior.

The ferroelectric properties and crystal structure of doped HfO2 thin films were investigated for different thicknesses, electrode materials, and annealing conditions. Metal-ferroelectric-metal capacitors containing Gd:HfO2 showed no reduction of the polarization within the studied thickness range, in contrast to hafnia films with other dopants. A qualitative model describing the influence of basic process parameters on the crystal structure of HfO2 was proposed. The influence of different structural parameters on the field cycling behavior was examined. This revealed the wake-up effect in doped HfO2 to be dominated by interface induced effects, rather than a field induced phase transition. TaN electrodes were shown to considerably enhance the stabilization of the ferroelectric phase in HfO2 compared to TiN electrodes, yielding a Pr of up to 35 μC/cm2. This effect was attributed to the interface oxidation of the electrodes during annealing, resulting in a different density of oxygen vacancies in the Gd:HfO2 films. Ab initio simulations confirmed the influence of oxygen vacancies on the phase stability of ferroelectric HfO2.

Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon-carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 μm) emerges through a successive alkyne-alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 μm).

One-shot double, triple, and quadruple borylation reactions of triarylamines were developed through a judicious choice of boron source and Brønsted base. With the aid of borylation reactions, a variety of BN-doped nanographenes were synthesized in two steps from commercially available starting materials. An organic light-emitting diode device employing BN-doped nanographene as an emitter exhibited deep pure-blue emission at 460 nm, with CIE coordinates of (0.13, 0.11), and an external quantum efficiency of 18.3%.

Carbon monoxide (CO) produced in many large-scale industrial oxidation processes is difficult to separate from nitrogen (N2), and afterward, CO is further oxidized to carbon dioxide. Here, we report a soft nanoporous crystalline material that selectively adsorbs CO with adaptable pores, and we present crystallographic evidence that CO molecules can coordinate with copper(II) ions. The unprecedented high selectivity was achieved by the synergetic effect of the local interaction between CO and accessible metal sites and a global transformation of the framework. This transformable crystalline material realized the separation of CO from mixtures with N2, a gas that is the most competitive to CO. The dynamic and efficient molecular trapping and releasing system is reminiscent of sophisticated biological systems such as heme proteins.

The PILATUS 1M detector is a hybrid pixel array detector with over one million pixels that operate in single photon counting mode. The detector, designed for macromolecular crystallography, is the largest pixel array detector currently in use at a synchrotron. It is a modular system consisting of 18 multichip modules covering an area of 21 cm x 24 cm. The design of the components as well as the manufacturing of the detector including the bump-bonding was performed at the Paul Scherrer Institute (PSI). The use of a single photon counting detector for protein crystallography requires detailed studies of the charge collection properties of the silicon sensor. The 18 modules are read out in parallel, leading to a full frame readout-time of 6.7 ms. This allows crystallographic data to be acquired in fine-varphi-slicing mode with continuous rotation of the sample. The detector was tested in several experiments at the protein crystallography beamline X06SA at the Swiss Light Source at PSI. Data were collected both in conventional oscillation mode using the shutter, as well as in a fine-varphi-slicing mode. After applying all the necessary corrections to data from a thaumatin crystal, the processing of the conventional data led to satisfactory merging R-factors of the order of 8.5%. This allows, for the first time, determination of a refined electron density map of a macromolecular biological crystal using a silicon pixel detector.

Earth's solid inner core is mainly composed of iron (Fe). Because the relevant ultrahigh pressure and temperature conditions are difficult to produce experimentally, the preferred crystal structure of Fe at the inner core remains uncertain. Static compression experiments showed that the hexagonal close-packed (hcp) structure of Fe is stable up to 377 gigapascals and 5700 kelvin, corresponding to inner core conditions. The observed weak temperature dependence of the c/a axial ratio suggests that hcp Fe is elastically anisotropic at core temperatures. Preferred orientation of the hcp phase may explain previously observed inner core seismic anisotropy.

The platinum-group metals (PGMs) are six neighboring elements in the periodic table of the elements. Each PGM can efficiently promote unique reactions, and therefore, alloying PGMs would create ideal catalysts for complex or multistep reactions that involve several reactants and intermediates. Thus, high-entropy-alloy (HEA) nanoparticles (NPs) of all six PGMs (denoted as PGM-HEA) having a great variety of adsorption sites on their surfaces could be ideal candidates to catalyze complex reactions. Here, we report for the first time PGM-HEA and demonstrate that PGM-HEA efficiently promotes the ethanol oxidation reaction (EOR) with complex 12-electron/12-proton transfer processes. PGM-HEA shows 2.5 (3.2), 6.1 (9.7), and 12.8 (3.4) times higher activity than the commercial Pd/C, Pd black and Pt/C catalysts in terms of intrinsic (mass) activity, respectively. Remarkably, it records more than 1.5 times higher mass activity than the most active catalyst to date. Our findings pave the way for promoting complex or multistep reactions that are seldom realized by mono- or bimetallic catalysts.

The unusual property of negative thermal expansion is of fundamental interest and may be used to fabricate composites with zero or other controlled thermal expansion values. Here we report that colossal negative thermal expansion (defined as linear expansion <−10−4 K−1 over a temperature range ~100 K) is accessible in perovskite oxides showing charge-transfer transitions. BiNiO3 shows a 2.6% volume reduction under pressure due to a Bi/Ni charge transfer that is shifted to ambient pressure through lanthanum substitution for Bi. Changing proportions of coexisting low- and high-temperature phases leads to smooth volume shrinkage on heating. The crystallographic linear expansion coefficient for Bi0.95La0.05NiO3 is −137×10−6 K−1 and a value of −82×10−6 K−1 is observed between 320 and 380 K from a dilatometric measurement on a ceramic pellet. Colossal negative thermal expansion materials operating at ambient conditions may also be accessible through metal-insulator transitions driven by other phenomena such as ferroelectric orders. Negative thermal expansion—contraction upon heating—is an unusual process that may be exploited to produce materials with zero or other controlled thermal expansion values. Azumaet al. observe negative thermal expansion in BiNiO3which is a result of Bi/Ni charge-transfer transitions.

We have determined the postspinel transformation boundary in Mg 2 SiO 4 by combining quench technique with in situ pressure measurements, using multiple internal pressure standards including Au, MgO, and Pt. The experimentally determined boundary is in general agreement with previous in situ measurements in which the Au scale of Anderson et al. [1989] was used to calculate pressure: Using this pressure scale, it occurs at significantly lower pressures compared to that corresponding to the 660‐km seismic discontinuity. In this study, we also report new experimental data on the transformation boundary determined using MgO as an internal standard. The results show that the transition boundary is located at pressures close to the 660‐km discontinuity using the MgO pressure scale of Speziale et al. [2001] and can be represented by a linear equation, P (GPa) = 25.12 − 0.0013 T (°C). The Clapeyron slope for the postspinel transition boundary is precisely determined and is significantly less negative than previous estimates. Our results, based on the MgO pressure scale, support the conventional hypothesis that the postspinel transformation is responsible for the observed 660‐km seismic discontinuity.

Bacteriorhodopsin (bR) is a light-driven proton pump and a model membrane transport protein. We used time-resolved serial femtosecond crystallography at an x-ray free electron laser to visualize conformational changes in bR from nanoseconds to milliseconds following photoactivation. An initially twisted retinal chromophore displaces a conserved tryptophan residue of transmembrane helix F on the cytoplasmic side of the protein while dislodging a key water molecule on the extracellular side. The resulting cascade of structural changes throughout the protein shows how motions are choreographed as bR transports protons uphill against a transmembrane concentration gradient.

The nanometer-size crystallization of poly(3,4-ethylenedioxythiophene) (PEDOT) inside the hydrophobic core region of PEDOT:PSS (PSS: poly(4-styrenesulfonate)) in a solid film is found by small and wide-angle X-ray scatterings using a synchrotron radiation source. The clarified PEDOT:PSS structure indicates that a nanocrystal of PEDOT surrounded by PSS is grown in the solid film from randomly oriented PEDOT in a micelle dispersed in water during the course of film fabrication. The addition of ethylene glycol (EG) to the PEDOT:PSS water dispersion and post-treatment of the pristine film with EG both provide similar improvements in PEDOT crystallinity. The crystallite size of PEDOT increases up to a comparable size (∼4.8 nm) to the hydrophobic PEDOT core region of the micelle. The electrical conductivity of the solid film is concurrently enhanced by 2 orders of magnitude with the growing nanocrystal of PEDOT. These findings clearly demonstrate the importance of the single crystalline PEDOT assisted by EG to obtain high electrical conductivity of the PEDOT:PSS solid film.

An application program to calculate various characteristics of synchrotron radiation, called SPECTRA, is described. The program does not need any other commercial software and is equipped with a full graphical user interface which makes data input quite easy. Equations on synchrotron radiation from arbitrary-field sources in a near-field region are derived, as are simplified expressions for ideal devices using a far-field approximation. Effective numerical methods implemented in SPECTRA to reduce computation time are explained, and several examples are presented.

Femtosecond x-ray laser pulses were used to probe micrometer-sized water droplets that were cooled down to 227 kelvin in vacuum. Isothermal compressibility and correlation length were extracted from x-ray scattering at the low-momentum transfer region. The temperature dependence of these thermodynamic response and correlation functions shows maxima at 229 kelvin for water and 233 kelvin for heavy water. In addition, we observed that the liquids undergo the fastest growth of tetrahedral structures at similar temperatures. These observations point to the existence of a Widom line, defined as the locus of maximum correlation length emanating from a critical point at positive pressures in the deeply supercooled regime. The difference in the maximum value of the isothermal compressibility between the two isotopes shows the importance of nuclear quantum effects.