Raman study of decomposition of Na-bearing carbonates in water fluid at high P-T parameters.

The study of Na-carbonates stability and their transformations in aqueous carbonate fluid under high P-T conditions is relevant from the point of view of the understanding geochemical processes of the Na-assisted carbon circulation in the Earth's crust and subduction zones. In situ Raman study of Na-bearing carbonate-water-Fe-metal system in diamond anvil cell (DAC) at high P-T conditions revealed that carbonates decompose with abiogenic formation of formates and other organic compounds that differs from behavior of carbonates in dry system. XRD and FTIR methods have been used additionally to determine the phase composition. Na-bearing carbonates (nahcolite NaHCO3, shortite Na2Ca2(CO3)3 and cancrinite Na7Ca[(CO3)1.5Al6Si6O24]⋅2H2O) in aqueous fluid decompose to form simple carbonates and formates (as dominant organic molecules) at moderate P-T parameters (above ∼0.2 GPa, 200 °C). Our experimental results directly confirm the hypothesis of Horita and Berndt (Science, 1999) about possible yield of organic formates in the carbonate-water-metal system. Nahcolite NaHCO3 in aqueous fluid in the presence of Fe metal decomposes into anhydrous phases: natrite γ-Na2CO3, siderite, magnetite (due to dissolution of Fe steel gasket), Na-formate and likely organic molecular crystalline solvate of Na-formate and methyl formate. Shortite decays into anhydrous phases: aragonite CaCO3, Na-Ca-formates and an amorphous phase. Cancrinite decomposes to unidentified carbonate-alumonosilicate phases, Na-Ca-formates and unknown organic molecular crystal. Magnetite is also formed in this system due to dissolution of Fe steel gasket used in DAC. The present study provides a new insight in processes of abiogenic formation of organic matter from carbonates in the crust and upper mantle.

Application of DUT-4 MOF structure switching for optical and electrical humidity sensing.

The threshold structural transformation of the DUT-4 metal-organic framework (MOF) from an ordered to distorted phase during exposure to ambient conditions has been revealed. The in situ X-ray diffraction analysis, in situ Raman and FTIR spectroscopy, scanning electron microscopy and synchronous thermal analysis have been used for investigation. The reversible effect of exposure time and humidity on such a phase transition has been confirmed. We also demonstrated that the observed phase transition correlated well with changes in the optical and electronic properties of DUT-4, paving the way to a new family of MOF-based phase change materials for optoelectronic applications.

Temperature phase transitions in silver niobate and lithium tantalate-modified silver niobate ceramics.

The temperature behaviour of 0.955 AgNbO3-0.045 LiTaO3 and AgNbO3 ceramics was studied in the range from 10 to 415 K using Raman spectroscopy. Ab initio calculations of the Raman spectra in the Pmc21 phase of AgNbO3 were carried out using three potentials (A-PZ, PBE, and PBEsol) for spectral interpretation. The peculiarities in the Raman spectra in AgNbO3 ceramics are observed and explained. The differences in the spectra of the 0.955 AgNbO3-0.045 LiTaO3 and AgNbO3 ceramics are shown. The temperatures of the structural changes in the 0.955 AgNbO3-0.45 LiTaO3 and AgNbO3 ceramics were discussed. A structural phase transition below 120 K was observed in silver niobate. A phase transition was observed at 310 K and below 150 K in 0.955 AgNbO3-0.045 LiTaO3.

Enhancement of Thermoelectric Performance in Bi0.5Sb1.5Te3 Particulate Composites Including Ferroelectric BaTiO3 Nanodots.

An increasing number of studies have reported producing composite structures by combining thermoelectric and functional materials. However, combining energy filtering and ferroelectric polarization to enhance the dimensionless figure of merit thermoelectric ZT remains elusive. Here we report a composite that contains nanostructured BaTiO3 embedded in a Bi0.5Sb1.5Te3 matrix. We show that ferroelectric BaTiO3 particles are evenly composited with Bi0.5Sb1.5Te3 grains reducing the concentration of free charge carriers with increasing BaTiO3 content. Additionally, as a result of the energy-filtering effect and ferroelectric polarization, the Seebeck coefficient was improved by ∼10% with a ∼10% improvement in power factors. The BaTiO3 phase can effectively scatters phonons reducing lattice thermal conductivity κl (0.5 W m-1 K-1) and increasing ZT to 1.31 at 363 K in Bi0.5Sb1.5Te3 composites with 2 vol % BaTiO3 content giving an improvement of ∼25% over pure Bi0.5Sb1.5Te3. Our work indicates that the introduction of ferroelectric nanoparticles is an effective method for optimizing the ZT of Bi0.5Sb1.5Te3-based thermoelectric materials.

The behavior of zeolites wairakite and phillipsite at high P-T parameters.

In situ investigation of mineral behavior in water medium at simultaneously high P-T parameters can be applied to modelling of mineral transformation processes in lithospheric plates. The behavior of zeolites wairakite and phillipsite under the P-T conditions of «cold¼ slab subduction, corresponding to the start of oceanic plate diving or ocean floor near geothermal sources, was studied by in situ Raman spectroscopy. During compression in water medium, phillipsite initial phase is stable up to T = 350 °C, P = 1.7 GPa and with further increase of P-T parameters, phillipsite undergoes amorphization and partially dissolves in water. Wairakite compressed in water medium has a polymorphic transformation at T ≈ 300 °C and P ≈ 0.4 GPa. At 300-450 °C and P = 1 GPa the Raman spectrum almost disappears due to the amorphization of wairakite. Zeolite wairakite partially dissolves, and other zeolite phillipsite grows out of the fluid at T = 450 °C and P = 1 GPa. This transformation indicates the higher stability of phillipsite in comparison to wairakite. The in situ observed high P-T stability of phillipsite, which does not transform to other zeolites, and its formation from wairakite may indicate ф possible widespread distribution of this zeolite in marine sediments. By using the plane-wave pseudo-potential method, ab initio DFT calculations of Raman and FTIR spectra of wairakite were carried out. Comparing theoretical and experimental spectra, interpretation of the vibrational spectra of both zeolites was suggested.

Structural phase transitions in flexible DUT-8(Ni) under high hydrostatic pressure.

The behaviours of the open pore (op) and closed pore (cp) phases of the flexible Ni2(ndc)2(dabco) (ndc - 2,6-naphthalene dicarboxylate, dabco - 1,4-diazabicyclo[2.2.2]octane, DUT-8(Ni)) metal-organic framework under high hydrostatic pressures up to 10 GPa in isopropanol and silicone oil were studied by Raman spectroscopy. Ab initio simulations of vibrational spectra were performed for the open and closed pore phases, which allowed us to disclose the characteristic vibrational modes affected by the structural transitions under pressure. Analysis of theoretical and experimental Raman data suggests that the op-cp transition involves gateway vibrations at 25 and 67 cm-1, corresponding to trampoline/rotational motions of aromatic linkers. The experiments reveal the formation of new distorted cp phases at pressures higher than 2 GPa, which are formed without amorphisation. The transition between the cp phase and the distorted cp phase is reversible. The experiments also reveal the pivotal role of the pressure transmitting medium on the phase transition behaviour.

Improvement of dielectric properties and energy storage performance in sandwich-structured P(VDF-CTFE) composites with low content of GO nanosheets.

Polymer-based dielectric capacitors play a notable part in the practical application of energy storage devices. Graphene oxide (GO) nanosheets can improve the dielectric properties of polymer-based composites. However, the breakdown strength will greatly reduce with the increase of GO content. Hence, the construction of sandwich structure can enhance the breakdown strength without reducing the dielectric constant. Herein, single-layered and sandwich-structured poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-CTFE)) nanocomposites with low content of GO nanosheets (<1.0 wt%) are prepared via employing a straightforward casting method. Compared with the single-layered composites and pure P(VDF-CTFE), the sandwich-structured composites exhibit comprehensively better performance compared. The sandwich-structured composite with 0.4 wt% GO nanosheets show an excellent dielectric constant of 13.6 (at 1 kHz) and an outstanding discharged energy density of 8.25 J cm-3at 3400 kV cm-1. These results demonstrate that the growth of the dielectric properties is owing to 2D GO nanosheets and the enhancement of breakdown strength due to the sandwich structure. The results from finite element simulation provide theoretical support for the design of high energy density composites.

Single particle Raman spectroscopy analysis of the metal-organic framework DUT-8(Ni) switching transition under hydrostatic pressure.

Experimental in situ observations of phase coexistence in switchable metal-organic frameworks are reported to provide a fundamental understanding of dynamic adsorbents that can change their pore structure in response to external stimuli. A prototypical flexible pillared layer framework DUT-8(Ni) (DUT = Dresden University of Technology) was studied under hydrostatic pressure by in situ Raman spectroscopy on single crystals. The closing transition of the open pore phase (op) containing DMF in the pores in silicon oil as a pressure transmitting fluid, as well as the closed pore phase (cp) to op transition under pressure in methanol, were studied. Phase coexistences during both transitions were observed.

Raman spectroscopy studies of the terahertz vibrational modes of a DUT-8 (Ni) metal-organic framework.

Low-frequency lattice vibrational modes have been discussed to play a crucial role in the phase transformation process of flexible metal-organic frameworks (MOFs). Therefore, Raman spectroscopy was applied to study the lattice dynamics of a pillared layer DUT-8(Ni) framework (DUT - Dresden University of Technology), existing in rigid and flexible forms. Both the open and the close pore phases could be unambiguously identified by breathing mode bands at 23 cm-1 and 60 cm-1 in the corresponding Raman spectra, showing the efficiency of the technique for monitoring the flexibility of MOF materials as well as the differences in the lattice vibrations of the two phases. Born-Oppenheimer Molecular Dynamics simulations showed that observed low-frequency bands indeed correspond to the oscillation of the breathing mode along the diagonals of the pore channels. Moreover, the directional character of low-frequency vibrations in the flexible version of DUT-8(Ni) could be visualized by the orientation dependent Raman spectroscopy experiment.

Pressure-induced phase transitions in crystalline L- and DL-cysteine.

A series of extended reversible phase transitions at approximately 0.1, 1.5, 2.0, and approximately 5 GPa was observed for the first time in the crystals of dl-cysteine by Raman spectroscopy. These are the first examples of the phase transitions induced by increasing pressure in the racemic crystal of an amino acid. In the crystals of the orthorhombic l-cysteine, a sequence of reversible structural changes in the pressure range between 1.1 and 3 GPa could be observed by Raman spectroscopy, instead of a single sharp phase transition at 1.9 GPa reported previously in ( Moggach, et al. Acta Crystallogr. 2006, B62, 296- 309 ). The role of the movements of the side -CH 2SH groups and of the changes in the hydrogen-bonding type in dl- and l-cysteine during the phase transitions with increasing pressure is discussed and compared with that on cooling down to 3 K.