Showing papers on "Phase (matter) published in 2015"
TL;DR: It is demonstrated that an N-terminal, arginine/glycine rich, intrinsically disordered protein (IDP) domain of LAF-1 is necessary and sufficient for both phase separation and RNA–protein interactions, and insight is provided into the mechanism by which IDP-driven molecular interactions give rise to liquid phase organelles with tunable properties.
Abstract: P granules and other RNA/protein bodies are membrane-less organelles that may assemble by intracellular phase separation, similar to the condensation of water vapor into droplets. However, the molecular driving forces and the nature of the condensed phases remain poorly understood. Here, we show that the Caenorhabditis elegans protein LAF-1, a DDX3 RNA helicase found in P granules, phase separates into P granule-like droplets in vitro. We adapt a microrheology technique to precisely measure the viscoelasticity of micrometer-sized LAF-1 droplets, revealing purely viscous properties highly tunable by salt and RNA concentration. RNA decreases viscosity and increases molecular dynamics within the droplet. Single molecule FRET assays suggest that this RNA fluidization results from highly dynamic RNA–protein interactions that emerge close to the droplet phase boundary. We demonstrate than an N-terminal, arginine/glycine rich, intrinsically disordered protein (IDP) domain of LAF-1 is necessary and sufficient for both phase separation and RNA–protein interactions. In vivo, RNAi knockdown of LAF-1 results in the dissolution of P granules in the early embryo, with an apparent submicromolar phase boundary comparable to that measured in vitro. Together, these findings demonstrate that LAF-1 is important for promoting P granule assembly and provide insight into the mechanism by which IDP-driven molecular interactions give rise to liquid phase organelles with tunable properties.
922 citations
TL;DR: In this article, the photoluminescence, transmittance, charge-carrier recombination dynamics, mobility, and diffusion length of CH3NH3PbI3 were investigated in the temperature range from 8 to 370 K.
Abstract: The photoluminescence, transmittance, charge-carrier recombination dynamics, mobility, and diffusion length of CH3NH3PbI3 are investigated in the temperature range from 8 to 370 K. Profound changes in the optoelectronic properties of this prototypical photovoltaic material are observed across the two structural phase transitions occurring at 160 and 310 K. Drude-like terahertz photoconductivity spectra at all temperatures above 80 K suggest that charge localization effects are absent in this range. The monomolecular charge-carrier recombination rate generally increases with rising temperature, indicating a mechanism dominated by ionized impurity mediated recombination. Deduced activation energies Ea associated with ionization are found to increase markedly from the room-temperature tetragonal (Ea ≈ 20 meV) to the higher-temperature cubic (Ea ≈ 200 meV) phase adopted above 310 K. Conversely, the bimolecular rate constant decreases with rising temperature as charge-carrier mobility declines, while the Auger rate constant is highly phase specific, suggesting a strong dependence on electronic band structure. The charge-carrier diffusion length gradually decreases with rising temperature from about 3 μm at -93 °C to 1.2 μm at 67 °C but remains well above the optical absorption depth in the visible spectrum. These results demonstrate that there are no fundamental obstacles to the operation of cells based on CH3NH3PbI3 under typical field conditions. The photoconductivity in CH3NH3PbI3 thin films is investigated from 8 to 370 K across three structural phases. Analysis of the charge-carrier recombination dynamics reveals a variety of starkly differing recombination mechanisms. Evidence of charge-carrier localization is observed only at low temperature. High charge mobility and diffusion length are maintained at high temperature beyond the tetragonal-to-cubic phase transition at ≈310 K.
778 citations
TL;DR: High-resolution electron microscopy imaging of water locked between two graphene sheets is reported, an archetypal example of hydrophobic confinement, and shows that the nanoconfined water at room temperature forms ‘square ice’—a phase having symmetry qualitatively different from the conventional tetrahedral geometry of hydrogen bonding between water molecules.
Abstract: Bulk water exists in many forms, including liquid, vapour and numerous crystalline and amorphous phases of ice, with hexagonal ice being responsible for the fascinating variety of snowflakes Much less noticeable but equally ubiquitous is water adsorbed at interfaces and confined in microscopic pores Such low-dimensional water determines aspects of various phenomena in materials science, geology, biology, tribology and nanotechnology Theory suggests many possible phases for adsorbed and confined water, but it has proved challenging to assess its crystal structure experimentally Here we report high-resolution electron microscopy imaging of water locked between two graphene sheets, an archetypal example of hydrophobic confinement The observations show that the nanoconfined water at room temperature forms 'square ice'--a phase having symmetry qualitatively different from the conventional tetrahedral geometry of hydrogen bonding between water molecules Square ice has a high packing density with a lattice constant of 283 A and can assemble in bilayer and trilayer crystallites Molecular dynamics simulations indicate that square ice should be present inside hydrophobic nanochannels independently of their exact atomic nature
584 citations
TL;DR: In this paper, the structural, thermal, and dielectric properties of the ferroelectric phase of HfO2, ZrO2 and Hf0.5O2 are investigated with carefully validated density functional computations.
Abstract: The structural, thermal, and dielectric properties of the ferroelectric phase of HfO2, ZrO2, and Hf0.5Zr0.5O2 (HZO) are investigated with carefully validated density functional computations. We find that the free bulk energy of the ferroelectric orthorhombic Pca21 phase is unfavorable compared to the monoclinic P21/c and the orthorhombic Pbca phase for all investigated stoichiometries in the Hf1−xZrxO2 system. To explain the existence of the ferroelectric phase in nanoscale thin films, we explore the Gibbs/Helmholtz free energies as a function of stress and film strain and find them unlikely to become minimal in HZO films for technological relevant conditions. To assess the contribution of surface energy to the phase stability, we parameterize a model, interpolating between existing data, and find the Helmholtz free energy of ferroelectric grains minimal for a range of size and stoichiometry. From the model, we predict undoped HfO2 to be ferroelectric for a grain size of about 4 nm and epitaxial HZO below 5 nm. Furthermore, we calculate the strength of an applied electric field necessary to cause the antiferroelectric phase transformation in ZrO2 from the P42/nmc phase as 1 MV/cm in agreement with experimental data, explaining the mechanism of field induced phase transformation.
528 citations
TL;DR: In a proof-of-concept demonstration for the obtained material's applications, highly efficient photocatalytic activity is achieved by simply hybridizing metallic N-MoS2 with semiconducting CdS nanorods due to the synergistic effect.
Abstract: Most recently, much attention has been devoted to 1T phase MoS2 because of its distinctive phase-engineering nature and promising applications in catalysts, electronics, and energy storage devices. While alkali metal intercalation and exfoliation methods have been well developed to realize unstable 1T-MoS2 , but the aqueous synthesis for producing stable metallic phase remains big challenging. Herein, a new synthetic protocol is developed to mass-produce colloidal metallic 1T-MoS2 layers highly stabilized by intercalated ammonium ions (abbreviated as N-MoS2). In combination with density functional calculations, the X-ray diffraction pattern and Raman spectra elucidate the excellent stability of metallic phase. As clearly depicted by high-angle annular dark-field imaging in an aberration-corrected scanning transmission electron microscope and extended X-ray absorption fine structure, the N-MoS2 exhibits a distorted octahedral structure with a 2a0 × a0 basal plane superlattice and 2.72 A Mo-Mo bond length. In a proof-of-concept demonstration for the obtained material's applications, highly efficient photocatalytic activity is achieved by simply hybridizing metallic N-MoS2 with semiconducting CdS nanorods due to the synergistic effect. As a direct outcome, this CdS:N-MoS2 hybrid shows giant enhancement of hydrogen evolution rate, which is almost 21-fold higher than pure CdS and threefold higher than corresponding annealed CdS:2H-MoS2.
470 citations
TL;DR: This approach resulted in improved structural and thermal stability in the severe cycling-test environment at 60 °C between 3.0 and 4.45 V and at elevated temperatures, showing a rate capability that was comparable to that of the pristine sample.
Abstract: Structural degradation of Ni-rich cathode materials (LiNixM1–xO2; M = Mn, Co, and Al; x > 0.5) during cycling at both high voltage (>4.3 V) and high temperature (>50 °C) led to the continuous generation of microcracks in a secondary particle that consisted of aggregated micrometer-sized primary particles. These microcracks caused deterioration of the electrochemical properties by disconnecting the electrical pathway between the primary particles and creating thermal instability owing to oxygen evolution during phase transformation. Here, we report a new concept to overcome those problems of the Ni-rich cathode material via nanoscale surface treatment of the primary particles. The resultant primary particles’ surfaces had a higher cobalt content and a cation-mixing phase (Fm3m) with nanoscale thickness in the LiNi0.6Co0.2Mn0.2O2 cathode, leading to mitigation of the microcracks by suppressing the structural change from a layered to rock-salt phase. Furthermore, the higher oxidation state of Mn4+ at the su...
441 citations
TL;DR: In this paper, the authors evaluated the properties of alginate-based edible films formed from nano-emulsions of essential oils (EOs) with different physical and functional properties.
433 citations
TL;DR: In this article, the structural, thermal, and dielectric properties of the ferroelectric phase of HfO$_2, ZrO_2$ and Hf$_{0.5}$ Zr$_{1-\chi}$ O$-2$ (HZO) are investigated with carefully validated density functional computations.
Abstract: The structural, thermal, and dielectric properties of the ferroelectric phase of HfO$_2$, ZrO$_2$ and Hf$_{0.5}$ Zr$_{0.5}$ O$_2$ (HZO) are investigated with carefully validated density functional computations. We find, that the free bulk energy of the ferroelectric orthorhombic Pca2$_{1}$ phase is unfavorable compared to the monoclinic P2$_{1}$/c and the orthorhombic Pbca phase for all investigated stoichiometries in the Hf$_{\chi}$Zr$_{1-\chi}$O$_2$ system. To explain the existence of the ferroelectric phase in nanoscale thin films we explore the Gibbs / Helmholtz free energies as a function of stress and film strain and find them unlikely to become minimal in HZO films for technological relevant conditions. To assess the contribution of surface energy to the phase stability we parameterize a model, interpolating between existing data, and find the Helmholtz free energy of ferroelectric grains minimal for a range of size and stoichiometry. From the model we predict undoped HfO$_2$ to be ferroelectric for a grain size of about 4 nm and epitaxial HZO below 5 nm. Furthermore we calculate the strength of an applied electric field necessary to cause the antiferroelectric phase transformation in ZrO$_2$ from the P4$_2$/nmc phase as 1 MV/cm in agreement with experimental data, explaining the mechanism of field induced phase transformation.
432 citations
TL;DR: This work explores the high-temperature dynamics of the disordered, one-dimensional XXZ model near the many-body localization (MBL) transition, focusing on the delocalized (i.e., "metallic") phase, and establishes scaling relations between the associated exponents, assuming a scaling form of the spin-diffusion propagator.
Abstract: We explore the high-temperature dynamics of the disordered, one-dimensional $XXZ$ model near the many-body localization (MBL) transition, focusing on the delocalized (i.e., ``metallic'') phase. In the vicinity of the transition, we find that this phase has the following properties: (i) local magnetization fluctuations relax subdiffusively; (ii) the ac conductivity vanishes near zero frequency as a power law; and (iii) the distribution of resistivities becomes increasingly broad at low frequencies, approaching a power law in the zero-frequency limit. We argue that these effects can be understood in a unified way if the metallic phase near the MBL transition is a quantum Griffiths phase. We establish scaling relations between the associated exponents, assuming a scaling form of the spin-diffusion propagator. A phenomenological classical resistor-capacitor model captures all the essential features.
354 citations
TL;DR: Colloidal nanoplatelets with predominantly single unit cell thickness and submicron lateral dimensions are obtained, which are stable in solution and exhibit a sharp excitonic absorption feature 0.5 eV blue-shifted from that of the three-dimensional bulk MAPbBr3 phase, representing a new addition to the growing family of colloidal two-dimensional nanostructures.
Abstract: We prepare colloidal nanoplatelets of methylammonium lead bromide (MAPbBr3) perovskite and compare the optical signatures of excitons in these two-dimensional systems to spherical perovskite nanocrystals and the corresponding bulk phase. We find that excitonic features that had previously been attributed to quantum confinement in MAPbBr3 nanocrystals are in fact a property of the bulk perovskite phase. Furthermore, we find that higher-energy absorption features originate from two-dimensional nanoplatelets, which are present in the nanocrystal reaction product. Upon further purification, we obtain colloidal nanoplatelets with predominantly single unit cell thickness and submicron lateral dimensions, which are stable in solution and exhibit a sharp excitonic absorption feature 0.5 eV blue-shifted from that of the three-dimensional bulk MAPbBr3 phase, representing a new addition to the growing family of colloidal two-dimensional nanostructures.
351 citations
TL;DR: In this article, thermally responsive and conductive hybrid hydrogels are synthesized by in situ formation of continuous network of conductive polymer hydrogel crosslinked by phytic acid in poly(N-isopropylacrylamide) matrix.
Abstract: Stimuli-responsive hydrogels with decent electrical properties are a promising class of polymeric materials for a range of technological applications, such as electrical, electrochemical, and biomedical devices. In this paper, thermally responsive and conductive hybrid hydrogels are synthesized by in situ formation of continuous network of conductive polymer hydrogels crosslinked by phytic acid in poly(N-isopropylacrylamide) matrix. The interpenetrating binary network structure provides the hybrid hydrogels with continuous transporting path for electrons, highly porous microstructure, strong interactions between two hydrogel networks, thus endowing the hybrid hydrogels with a unique combination of high electrical conductivity (up to 0.8 S m−1), high thermoresponsive sensitivity (significant volume change within several seconds), and greatly enhanced mechanical properties. This work demonstrates that the architecture of the filling phase in the hydrogel matrix and design of hybrid hydrogel structure play an important role in determining the performance of the resulting hybrid material. The attractive performance of these hybrid hydrogels is further demonstrated by the developed switcher device which suggests potential applications in stimuli-responsive electronic devices.
TL;DR: In this paper, the structural and optical properties of CH3NH3PbI3 from room temperature to 5 K were investigated, and X-ray diffraction reveals an extremely sharp transition at 163 K from a twinned tetragonal I4/mcm phase to a low temperature phase characterized by complex twinning and possible frozen disorder.
Abstract: Hybrid organometal halide perovskites have been demonstrated to have outstanding performance as semiconductors for solar energy conversion. Further improvement of the efficiency and stability of these devices requires a deeper understanding of their intrinsic photophysical properties. Here, the structural and optical properties of high-quality single crystals of CH3NH3PbI3 from room temperature to 5 K are investigated. X-ray diffraction reveals an extremely sharp transition at 163 K from a twinned tetragonal I4/mcm phase to a low-temperature phase characterized by complex twinning and possible frozen disorder. Above the transition temperature, the photoluminescence is in agreement with a band-edge transition, explaining the outstanding performances of the solar cells. Whereas below the transition temperature, three different excitonic features arise, one of which is attributed to a free-exciton and the other two to bound excitons (BEs). The BEs are characterized by a decay dynamics of about 5 μs and by a saturation phenomenon at high power excitation. The long lifetime and the saturation effect make us attribute these low temperature features to bound triplet excitons. This results in a description of the room temperature recombination as being due to spontaneous band-to-band radiative transitions, whereas a diffusion-limited behavior is expected for the low-temperature range.
TL;DR: In this paper, a detailed analysis of the relevant interfaces using surface science methods is presented, including the IL/vacuum or IL/gas interface, the solubility and surface enrichment of dissolved metal complexes, the support interface and the in situ monitoring of chemical reactions in ionic liquids are presented.
Abstract: Ionic liquids (ILs), salts with melting points below 100 °C, represent a fascinating class of liquid materials typically characterized by an extremely low vapor pressure. Besides their application as new solvents or as electrolytes for electrochemical purposes, there are two important concepts of using ILs in catalysis: Liquid–liquid biphasic catalysis and IL thin film catalysis. Liquid–liquid biphasic catalysis enables either a very efficient manner to apply catalytic ILs, e.g. in Friedel–Crafts reactions, or to apply ionic transition metal catalyst solutions. In both cases, phase separation after reaction allows an easy separation of reaction products and catalyst re-use. One problem of liquid–liquid biphasic catalysis is mass transfer limitation. If the chemical reaction is much faster than the liquid–liquid mass transfer the latter limits the overall reaction rate. This problem is overcome in IL thin film catalysis where diffusion pathways and thus the characteristic time of diffusion are short. Here, Supported Ionic Liquid Phase (SILP) and Solid Catalyst with Ionic Liquid Layer (SCILL) are the two most important concepts. In both, a high surface area solid substrate is covered with a thin IL film, which contains either a homogeneously dissolved transition metal complex for SILP, or which modifies catalytically active surface sites at the support for SCILL. In each concept, interface phenomena play a very important role: These may concern the interface of an IL phase with an organic phase in the case of liquid–liquid biphasic catalysis. For IL thin film catalysis, the interfaces of the IL with the gas phase and with catalytic nanoparticles and/or support materials are of critical importance. It has recently been demonstrated that these interfaces and also the bulk of ILs can be investigated in great detail using surface science studies, which greatly contributed to the fundamental understanding of the catalytic properties of ILs and supported IL materials. Exemplary results concerning the IL/vacuum or IL/gas interface, the solubility and surface enrichment of dissolved metal complexes, the IL/support interface and the in situ monitoring of chemical reactions in ILs are presented. Important concepts in catalysis with ionic liquids are reviewed, including Supported Ionic Liquid Phase (SILP) and Solid Catalyst with Ionic Liquid Layer (SCILL), along with the detailed analysis of the relevant interfaces using surface science methods.
TL;DR: It is shown that intrinsically disordered, repeat proteins can be designed to exhibit tunable lower or upper critical solution temperature transitions in physiological solutions and that mutation of key residues at the repeat level abolishes phase behaviour or encodes an orthogonal transition.
Abstract: Proteins and synthetic polymers that undergo aqueous phase transitions mediate self-assembly in nature and in man-made material systems. Yet little is known about how the phase behaviour of a protein is encoded in its amino acid sequence. Here, by synthesizing intrinsically disordered, repeat proteins to test motifs that we hypothesized would encode phase behaviour, we show that the proteins can be designed to exhibit tunable lower or upper critical solution temperature (LCST and UCST, respectively) transitions in physiological solutions. We also show that mutation of key residues at the repeat level abolishes phase behaviour or encodes an orthogonal transition. Furthermore, we provide heuristics to identify, at the proteome level, proteins that might exhibit phase behaviour and to design novel protein polymers consisting of biologically active peptide repeats that exhibit LCST or UCST transitions. These findings set the foundation for the prediction and encoding of phase behaviour at the sequence level.
TL;DR: A combination of operando X-ray diffraction, pair distribution function (PDF) analysis coupled with electrochemical measurements and Mossbauer spectroscopy elucidates the nature of the phase transitions induced by insertion and extraction of sodium ions in P2-Na0.5O2 as discussed by the authors.
Abstract: A combination of operando X-ray diffraction, pair distribution function (PDF) analysis coupled with electrochemical measurements and Mossbauer spectroscopy elucidates the nature of the phase transitions induced by insertion and extraction of sodium ions in P2-Na0.67[NiyMn0.5+yFe0.5−2y]O2 (y = 0, 0.10, 0.15). When phase transitions are avoided, the optimal cathode material – P2-Na0.67Fe0.2Mn0.65Ni0.15O2 – delivers 25% more energy than the unsubstituted material, sustaining high specific energy (350 Wh kg−1) at moderate rates and maintains 80% of the original energy density after 150 cycles – a significant improvement in performance vs. the unsubstituted analogue. The crystal structure of the high voltage phase is solved for the first time by X-ray PDF analysis of P2-Na0.67−zFe0.5Mn0.5O2 (where z ∼ 0.5), revealing that migration of the transition metals – particularly Fe3+ – into tetrahedral sites in the interlayer space occurs at high potential. This results in new short range order between two adjacent layers. Although the transition metal migration is reversible as proven by electrochemical performance, it induces a large disfavourable cell polarization. The deleterious high voltage transition is mitigated by substitution of Fe3+ by Mn4+/Ni2+, giving rise to better cycling performance. Moreover, as demonstrated by 57Fe Mossbauer spectroscopy, the much lower ratio of Fe4+O6 to Fe3+O6 observed systematically across the range of Ni content – compared to the values expected from a purely ionic model – suggests redox activity involves the O-2p orbitals owing to their overlap with the transition metal-3d orbitals.
TL;DR: The phase transition of single layer molybdenum disulfide (MoS2) from semiconducting 2H to metallic 1T and then to 1T′ phases, and the effect of the phase transition on hydrogen evolution reaction (HER) are investigated within this work by density functional theory as discussed by the authors.
Abstract: The phase transition of single layer molybdenum disulfide (MoS2) from semiconducting 2H to metallic 1T and then to 1T′ phases, and the effect of the phase transition on hydrogen evolution reaction (HER) are investigated within this work by density functional theory. Experimentally, 2H-MoS2 has been widely used as an excellent electrode for HER and can get charged easily. Here we find that the negative charge has a significant impact on the structural phase transition in a MoS2 monolayer. The thermodynamic stability of 1T-MoS2 increases with the negative charge state, comparing with the 2H-MoS2 structure before phase transition and the kinetic energy barrier for a phase transition from 2H to 1T decreases from 1.59 to 0.27 eV when 4e– are injected per MoS2 unit. Additionally, 1T phase is found to transform into the distorted structure (1T′ phase) spontaneously. On their activity toward hydrogen evolution reaction, 1T′-MoS2 structure shows comparable hydrogen evolution reaction activity to the 2H-MoS2 struct...
TL;DR: In this paper, a detailed phase transformation pathway in the LMR cathode (Li[Li 0.2Ni0.2Mn0.6]O2) during cycling for samples prepared by the hydrothermal assisted (HA) method is reported.
Abstract: Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, the voltage fading mechanism in these materials as well as its relationships to fundamental structural changes is far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for samples prepared by the hydrothermal assisted (HA) method. It is found that the transformation pathway of the LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that the LMR cathode prepared by the HA approach experiences a phase transformation from the layered structure (initial C2/m phase transforms to R3m phase after activation) to a LT-LiCoO2 type defect spinel-like structure (with the Fd3m space group) and then to a disordered rock-salt structure (with the Fm3m space group). The voltage fade can be well correlated with Li ion i...
TL;DR: It is found that phase separation from an initially disordered mixture can occur with as little as 15% of the particles being active, and it is shown that a system prepared in a suitable fully segregated initial state reproducibly self-assembles an active "corona," which triggers crystallization of the passive core by initiating a compression wave.
Abstract: We investigate the phase behavior and kinetics of a monodisperse mixture of active (i.e., self-propelled) and passive isometric Brownian particles through Brownian dynamics simulations and theory. As in a purely active system, motility of the active component triggers phase separation into a dense and a dilute phase; in the dense phase we further find active-passive segregation, with "rafts" of passive particles in a "sea" of active particles. We find that phase separation from an initially disordered mixture can occur with as little as 15 percent of the particles being active. Finally, we show that a system prepared in a suitable fully segregated initial state reproducibly self-assembles an active "corona" which triggers crystallization of the passive core by initiating a compression wave. Our findings are relevant to the experimental pursuit of directed self-assembly using active particles. (Less)
TL;DR: It is reported that graphite-phase polymeric carbon nitride could be dissolved in concentrated sulfuric acid, the first feasible solvent so far, due to the synergistic protonation and intercalation, and the first successful liquid-state NMR spectra of GPPCN were obtained.
Abstract: Graphite-phase polymeric carbon nitride (GPPCN) has emerged as a promising metal-free material toward optoelectronics and (photo)catalysis. However, the insolubility of GPPCN remains one of the biggest impediments toward its potential applications. Herein, we report that GPPCN could be dissolved in concentrated sulfuric acid, the first feasible solvent so far, due to the synergistic protonation and intercalation. The concentration was up to 300 mg/mL, thousands of time higher than previous reported dispersions. As a result, the first successful liquid-state NMR spectra of GPPCN were obtained, which provides a more feasible method to reveal the finer structure of GPPCN. Moreover, at high concentration, a liquid crystal phase for the carbon nitride family was first observed. The successful dissolution of GPPCN and the formation of highly anisotropic mesophases would greatly pave the potential applications such as GPPCN-based nanocomposites or assembly of marcroscopic, ordered materials.
TL;DR: The Chevrel phase Mo6S8 was prepared by reaction of CuCl2 and (NH4)2MoS4 in DMF (90 °C, 6 h) followed by heating of the precipitate in 5% H2/Ar atmosphere (1000 °C 7 h) as discussed by the authors.
Abstract: The Chevrel phase Mo6S8 is prepared by reaction of CuCl2 and (NH4)2MoS4 in DMF (90 °C, 6 h) followed by heating of the precipitate in 5% H2/Ar atmosphere (1000 °C, 7 h).
TL;DR: The results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.
Abstract: Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH3NH3PbBr3 (MAPbBr3), under hydrostatic pressure up to 34 GPa at room temperature. Two phase transformations below 2 GPa (from Pm3m to Im3, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr6 octahedra and destroying of long-range ordering of MA cations, respectively. The visible light response of MAPbBr3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorph...
TL;DR: In this article, the buckled antimonene has been shown to exhibit strong directional mechanical properties, which may give rise to a strong influence of strain on the electronic properties of antimony.
Abstract: The pseudolayered character of 3D bulk crystals of antimony has led us to predict its 2D single-layer crystalline phase named antimonene in a buckled honeycomb structure like silicene. Sb atoms also form an asymmetric washboard structure like black phospherene. Based on an extensive analysis comprising ab initio phonon and finite-temperature molecular dynamics calculations, we show that these two single-layer phases are robust and can remain stable at high temperatures. They are nonmagnetic semiconductors with band gaps ranging from 0.3 eV to 1.5 eV, and are suitable for 2D electronic applications. The washboard antimonene displays strongly directional mechanical properties, which may give rise to a strong influence of strain on the electronic properties. Single-layer antimonene phases form bilayer and trilayer structures with wide interlayer spacings. In multilayers, this spacing is reduced and eventually the structure changes to 3D pseudolayered bulk crystals. The zigzag and armchair nanoribbons of the antimonene phases have fundamental band gaps derived from reconstructed edge states and display a diversity of magnetic and electronic properties depending on their width and edge geometry. Their band gaps are tunable with the widths of the nanoribbons. When grown on substrates, such as germanene or Ge(111), the buckled antimonene attains a significant influence of substrates.
TL;DR: In this paper, the potential of chemical functionalization of monolayer MoS2 in tuning its electronic properties by first-principles density functional theory was investigated and it was shown that the chemical bonding of the functional groups (H, CH3, CF3, OCH3, NH2) is anomalously strong on the 1T phase (in low-coverage regimes) but very weak on the 2H phase.
Abstract: The MoS2 monolayer is the second most studied two-dimensional material after graphene. However, the covalent chemistry through the S layers has not been fully explored for controlling the properties of the MoS2 monolayer. Herein we probe the potential of chemical functionalization of monolayer MoS2 in tuning its electronic properties by first-principles density functional theory. We find that the chemical bonding of the functional groups (H, CH3, CF3, OCH3, NH2) is anomalously strong (4–5 eV) on the 1T phase (in low-coverage regimes) but very weak on the 2H phase. This strong affinity of 1T-MoS2 for functional groups is closely related to its metallicity and partially filled Mo 4d states. More interestingly, 1T-MoS2, which is metastable when unfunctionalized, becomes the stable phase after a crossover coverage of functionalization. Surface functionalization also results in dramatic changes to the electronic properties of 1T-MoS2. We find that the band gap of the 1T-MoS2 monolayer strongly depends on the f...
TL;DR: In this article, X-ray fluorescence analysis and dielectric properties analysis indicate that rhombohedral polar phase and tetragonal weakly polar phase coexist in BNTBT-xNN ceramics at room temperature.
Abstract: (1 − x)BNTBT-xNN ceramics were prepared by conventional solid state reaction method. X-ray fluorescence analysis shows that the volatilization of Na element occurs during sintering process, the resulted concentration variation of V ′ Na − V O − V ′ Na defect dipoles facilitate the grain growth. XRD analysis and dielectric properties analysis indicate that rhombohedral polar phase and tetragonal weakly polar phase coexist in BNTBT ceramics at room temperature. By increasing the NN amount, the rhombohedral polar phase content sharply decreases, leading to a smaller remnant polarization. The dielectric anomaly corresponding to the depolarization temperature disappears from the temperature range investigated. According to the XRD results, the amount of tetragonal weakly polar phase decreases with increasing NN content and the structure evolves toward a pseudocubic symmetry. The phase structure change results in more slim P–E loops. The optimum energy storage properties was obtained for the composition of x = 0.10, with energy storage density of 0.71 J/cm3 at 7 kV/mm and a good temperature stability around 25–150 °C.
11 Nov 2015-Materials Science and Engineering A-structural Materials Properties Microstructure and Processing
TL;DR: In this article, the effects of Al on microstructure and mechanical properties of AlxCoCrFeNi (x=0.1, 0.75 and 1.5) high-entropy alloys were systematically studied by using various characterization methods.
Abstract: The effects of Al on microstructure and mechanical properties of AlxCoCrFeNi (x=0.1, 0.75 and 1.5) high-entropy alloys were systematically studied by using various characterization methods. It was found that the crystalline structure of AlxCoCrFeNi high-entropy alloy varies markedly with Al content, which changes from the initial single face-centered cubic (fcc) to fcc plus ordered body-centered cubic (bcc) structure (B2) and then to a duplex bcc structure (A2+B2) as the Al content is increased. The chemical composition analysis reveals that Al primarily partitions to B2 phase, suggesting Al is a stabilizer of B2 structure. With increasing Al content, more Ni and Al partition to the B2 phase due to the very negative mixing enthalpy of Ni and Al, and another phase enriched in Cr and Fe transforms from fcc to disordered bcc. Nano indentation measurements show that the hardness of AlxCoCrFeNi high-entropy alloy increases with Al content, accompanied by the decrease of ductility. The stability of single-phase solid solution in AlxCoCrFeNi HEAs is deduced from various criteria. Combined with the experiment results of other similar HEA systems, such as AlxCoCrFeNiCu, the effects of Al addition on the microstructure of AlxCoCrFeNi HEAs are discussed based on the Gibbs free energy of all competing phases and the fundamental properties of constituent elements. The aim of current study is to provide experimental evidence to establish a correlation between the microstructure and mechanical properties to search for high-entropy alloys with higher performances.
TL;DR: In this article, a cellulose sponge with stable superoleophobicity under water and superhydrophilic wettability under oil without any further chemical modification for oil-water emulsion separation is presented.
TL;DR: This work presents a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties, and describes how phase purity can be controlled.
Abstract: Superparamagnetic iron oxide nanoparticles (SPIONs) are used for a wide range of biomedical applications requiring precise control over their physical and magnetic properties, which are dependent on their size and crystallographic phase. Here we present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties. We investigate critical parameters for synthesis of monodisperse SPIONs by organic thermal decomposition. Three different, commonly used, iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) are evaluated under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2–30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution, phase, and magnetic properties. In particular, large quantities of excess surfactant (up to 25 : 1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase, in addition to nanoparticle size and shape, is critical for establishing magnetic properties such as differential susceptibility (dm/dH) and anisotropy. As an example, we show the importance of obtaining the required size and iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled. These results provide much of the information necessary to determine which iron oxide synthesis protocol is best suited to a particular application.
TL;DR: In this article, the authors extend the notion of phase transformations to periodic cellular materials by introducing materials whose unit cells have multiple stable configurations, each stable configuration corresponds to a stable phase, and transitions between these phases are regarded as phase transformations of the cellular material.
TL;DR: A comprehensive and up-to-date review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes is reported.
Abstract: The lipid cubic phase or in meso method is a robust approach for crystallizing membrane proteins for structure determination. The uptake of the method is such that it is experiencing what can only be described as explosive growth. This timely, comprehensive and up-to-date review introduces the reader to the practice of in meso crystallogenesis, to the associated challenges and to their solutions. A model of how crystallization comes about mechanistically is presented for a more rational approach to crystallization. The possible involvement of the lamellar and inverted hexagonal phases in crystallogenesis and the application of the method to water-soluble, monotopic and lipid-anchored proteins are addressed. How to set up trials manually and automatically with a robot is introduced with reference to open-access online videos that provide a practical guide to all aspects of the method. These range from protein reconstitution to crystal harvesting from the hosting mesophase, which is noted for its viscosity and stickiness. The sponge phase, as an alternative medium in which to perform crystallization, is described. The compatibility of the method with additive lipids, detergents, precipitant-screen components and materials carried along with the protein such as denaturants and reducing agents is considered. The powerful host and additive lipid-screening strategies are described along with how samples that have low protein concentration and cell-free expressed protein can be used. Assaying the protein reconstituted in the bilayer of the cubic phase for function is an important element of quality control and is detailed. Host lipid design for crystallization at low temperatures and for large proteins and complexes is outlined. Experimental phasing by heavy-atom derivatization, soaking or co-crystallization is routine and the approaches that have been implemented to date are described. An overview and a breakdown by family and function of the close to 200 published structures that have been obtained using in meso-grown crystals are given. Recommendations for conducting the screening process to give a more productive outcome are summarized. The fact that the in meso method also works with soluble proteins should not be overlooked. Recent applications of the method for in situ serial crystallography at X-ray free-electron lasers and synchrotrons are described. The review ends with a view to the future and to the bright prospects for the method, which continues to contribute to our understanding of the molecular mechanisms of some of nature's most valued proteinaceous robots.