21 research outputs found
Thin films of unsubstituted and fluorinated palladium phthalocyanines: structure and sensor response toward ammonia and hydrogen
In the present work, we study and compare the structure and sensing properties of thin films of unsubstituted palladium phthalocyanine (PdPc) and hexadecafluorosubstituted palladium phthalocyanine (PdPcF16). Thin films of PdPc and PdPcF16 were obtained by the method of organic molecular beam deposition and their structure was studied using UV-visible spectroscopy, X-ray diffraction and atomic force microscopy techniques. The electrical sensor response of PdPc films toward ammonia and hydrogen was investigated and compared with that of PdPcF16 films. The nature of interaction between the phthalocyanines films and some gaseous analyte molecules has been clarified using Quantum chemical (DFT) calculations
Effect of fluorosubstitution on the structure of single crystals, Effect of fluorosubstitution on the structure of single crystals,thin films and spectral properties of palladium phthalocyanines
In this work, the crystalline structure of single crystals grown by vacuum sublimation of unsubstituted palladium phthalocyanines (PdPc), its tetrafluorinated (PdPcF4) and hexadecafluorinated (PdPcF16) derivatives have been investigated using X-ray diffraction measurements. Two crystalline phases have been identified for PdPc; the molecules in both phases crystallize in stacks with herringbone arrangement in the monoclinic space groups (C2/c for -PdPc; P21/n for -PdPc). Both PdPcF4 and PdPcF16 crystallize in the triclinic P-1 space group, forming stacks of molecules in columnar arrangement with molecules in adjacent columns are aligned parallel to one another. X-ray diffraction measurements have also been used to elucidate the structural features and molecular orientation of thin films of PdPc, PdPcF4 and PdPcF16, grown by organic molecular beam deposition at different substrate temperatures. The effect of fluorosubstitution on UV-visible optical absorption and vibrational spectra of palladium phthalocyanine derivatives is also discussed
Solid-State Transformations of Mayenite and Core-Shell Structures of C12A7@C Type at High Pressure, High Temperature Conditions
Calcium aluminate of a mayenite structure, 12CaO∙7Al2O3 (C12A7), is widely applicable in many fields of modern science and technology. Therefore, its behavior under various experimental conditions is of special interest. The present research aimed to estimate the possible impact of the carbon shell in core-shell materials of C12A7@C type on the proceeding of solid-state reactions of mayenite with graphite and magnesium oxide under High Pressure, High Temperature (HPHT) conditions. The phase composition of the solid-state products formed at a pressure of 4 GPa and temperature of 1450 °C was studied. As is found, the interaction of mayenite with graphite under such conditions is accompanied by the formation of an aluminum-rich phase of the CaO∙6Al2O3 composition, while in the case of core-shell structure (C12A7@C), the same interaction does not lead to the formation of such a single phase. For this system, a number of hardly identified calcium aluminate phases along with the carbide-like phrases have appeared. The main product of the interaction of mayenite and C12A7@C with MgO under HPHT conditions is the spinel phase Al2MgO4. This indicates that, in the case of the C12A7@C structure, the carbon shell is not able to prevent the interaction of the oxide mayenite core with magnesium oxide located outside the carbon shell. Nevertheless, the other solid-state products accompanying the spinel formation are significantly different for the cases of pure C12A7 and C12A7@C core-shell structure. The obtained results clearly illustrate that the HPHT conditions used in these experiments lead to the complete destruction of the mayenite structure and the formation of new phases, which compositions differ noticeably depending on the precursor used—pure mayenite or C12A7@C core-shell structure
Fluorinated Metal Phthalocyanines: Interplay between Fluorination Degree, Films Orientation, and Ammonia Sensing Properties
In this work, the sensor response of MPcFx (M = Cu, Co, Zn; x = 0, 4, 16) films toward gaseous NH3 (10–50 ppm) was studied by a chemiresistive method and compared to that of unsubstituted MPc films to reveal the effects of central metals and F-substituents on the sensing properties. A combination of atomic force microscopy and X-ray diffraction techniques have been used to elucidate the structural features of thin MPcFx films deposited by organic molecular beam deposition. It has been shown that the sensor response of MPcF4 films to ammonia is noticeably higher than that of MPc films, which is in good correlation with the values of binding energy between the metal phthalocyanine and NH3 molecules, as calculated by the density functional theory (DFT) method. At the same time, in contrast to the DFT calculations, MPcF16 demonstrated the lesser sensor response compared with MPcF4, which appeared to be connected with the different structure and morphology of their films. The ZnPcF4 films were shown to exhibit a sensitivity to ammonia up to concentrations as low as 0.1 ppm, and can be used for the selective detection of ammonia in the presence of some reducing gases and volatile organic compounds. Moreover, the ZnPcF4 films can be used for the detection of NH3 in the gas mixture simulating exhaled air (N2 76%, O2 16%, H2O 5%, and CO2 3%)
Synthesis and Crystal Chemistry of Octahedral Rhodium(III) Chloroamines
Rhodium(III) octahedral complexes with amine and chloride ligands are the most common starting compounds for preparing catalytically active rhodium(I) and rhodium(III) species. Despite intensive study during the last 100 years, synthesis and crystal structures of rhodium(III) complexes were described only briefly. Some [RhClx(NH3)6-x] compounds are still unknown. In this study, available information about synthetic protocols and the crystal structures of possible [RhClx(NH3)6−x] octahedral species are summarized and critically analyzed. Unknown crystal structures of (NH4)2[Rh(NH3)Cl5], trans–[Rh(NH3)4Cl2]Cl⋅H2O, and cis–[Rh(NH3)4Cl2]Cl are reported based on high quality single crystal X-ray diffraction data. The crystal structure of [Rh(NH3)5Cl]Cl2 was redetermined. All available crystal structures with octahedral complexes [RhClx(NH3)6-x] were analyzed in terms of their packings and pseudo-translational sublattices. Pseudo-translation lattices suggest face-centered cubic and hexagonal closed-packed sub-cells, where Rh atoms occupy nearly ideal lattices
Porous Natural Diamond with Embedded Metal (Pt<sub>0.50</sub>–Co<sub>0.50</sub>)
Natural diamond crystals with a highly porous surface were used as substrates for synthesizing single-phase bimetallic Pt–Co nanoparticles at temperatures of 500 °C and 800 °C. The metal nanoparticles inside the pores were determined to take the form of single-phase Pt0.50Co0.50 solid solutions with different degrees of superstructure ordering. A detailed characterization of both nanoalloys revealed a tetragonal symmetry with a space group, P4/mmm. For the sample obtained at 500 °C, the lattice parameters were a = 2.673(2), c = 3.735(3) Å, and c/a = 1.397(1); for the samples obtained at 800 °C, the parameters were—a = 2.688(2), c = 3.697(3) Å, and c/a = 1.375(1). Within the experimental parameters, no significant chemical interaction of the diamond with the Pt–Co particles was identified. The results demonstrate a strong anchoring effect of the metallic material within the etching pores. The successful synthesis of bimetallic Pt–Co particles embedded inside the caverns can facilitate a study of their magnetic properties. The presence of Pt–Co in specific diamond compositions can also be used for marking diamond crystals as a means for their subtle identification, as well as confirming the possibility of capturing significant amounts of metal along with diamonds during their dissolution in the deep Earth
HPHT-Treated Impact Diamonds from the Popigai Crater (Siberian Craton): XRD and Raman Spectroscopy Evidence
Phase change and graphitization of diamonds from the Popigai impact crater (Krasnoyarsk Territory, Siberian platform, Russia) exposed to high-pressure high-temperature (HPHT) conditions of 5.5 GPa and 2000–2200 °C are studied by Raman spectroscopy and X-ray diffractometry (XRD). Light-color diamonds of type 1, free from inclusions, with 0 to 10 % lonsdaleite, are more resistant to HPHT effects than dark diamonds of type 2 rich in lonsdaleite and graphite. The lonsdaleite/diamond ratios in lonsdaleite-bearing impact diamonds become smaller upon annealing, possibly because lonsdaleite transforms to cubic diamond simultaneously with graphitization. Therefore, lonsdaleite is more likely a structure defect in diamond than a separate hexagonal phase
Equations of state of rhodium, iridium and their alloys up to 70 GPa
Knowledge of the compressional and thermal behaviour of metals and alloys is of a high fundamental and applied value. In this work, we studied the behaviour of Ir, Rh, and their fcc-structured alloys, IrRh and IrOsPtRhRu, up to 70 GPa using the diamond anvil cell technique with synchrotron X-ray diffraction. We found that all these materials are structurally stable upon room-temperature hydrostatic compression in the whole pressure interval, as well as upon heating to 2273 K both at ambient and high pressure. Rh, IrRh and IrOsPtRhRu were investigated under static compression for the first time. According to our data, the compressibility of Ir, Rh, fcc–IrRh, and fcc–IrOsPtRhRu, can be described with the 3rd order Birch-Murnaghan equation of state with the following parameters: V = 14.14(6) Å·atom, B = 341(10) GPa, and B0' = 4.7(3); V = 13.73(7) Å·atom, B = 301(9) GPa, and B' = 3.1(2); V = 13.90(8) Å·atom, B = 317(17) GPa, and B' = 6.0(5); V = 14.16(9) Å·atom, B = 300(22) GPa, B' = 6(1), where V is the unit cell volume, B and B' – are the bulk modulus and its pressure derivative
In Situ Observations of Blistering of a Metal Irradiated with 2-MeV Protons
A vacuum-insulated tandem accelerator was used to observe in situ blistering during 2-MeV proton irradiation of metallic samples to a fluence of up to 6.7 × 1020 cm−2. Samples consisting of copper of different purity, tantalum and tantalum-copper compounds were placed on the proton beam path and forced to cool. The surface state of the samples was observed using a charge-coupled device camera with a remote microscope. Thermistors, a pyrometer and an infrared camera were applied to measure the temperature of the samples during irradiation. After irradiation, the samples were analyzed on an X-ray diffractometer, laser and electron microscopes. The present study describes the experiment, presents the results obtained and notes their relevance and significance in the development of a lithium target for an accelerator-based neutron source, for use in boron neutron capture therapy of cancer
Face-Centered Cubic Refractory Alloys Prepared from Single-Source Precursors
Three binary fcc-structured alloys (fcc–Ir0.50Pt0.50, fcc–Rh0.66Pt0.33 and fcc–Rh0.50Pd0.50) were prepared from [Ir(NH3)5Cl][PtCl6], [Ir(NH3)5Cl][PtBr6], [Rh(NH3)5Cl]2[PtCl6]Cl2 and [Rh(NH3)5Cl][PdCl4]·H2O, respectively, as single-source precursors. All alloys were prepared by thermal decomposition in gaseous hydrogen flow below 800 °C. Fcc–Ir0.50Pt0.50 and fcc–Rh0.50Pd0.50 correspond to miscibility gaps on binary metallic phase diagrams and can be considered as metastable alloys. Detailed comparison of [Ir(NH3)5Cl][PtCl6] and [Ir(NH3)5Cl][PtBr6] crystal structures suggests that two isoformular salts are not isostructural. In [Ir(NH3)5Cl][PtBr6], specific Br…Br interactions are responsible for a crystal structure arrangement. Room temperature compressibility of fcc–Ir0.50Pt0.50, fcc–Rh0.66Pt0.33 and fcc–Rh0.50Pd0.50 has been investigated up to 50 GPa in diamond anvil cells. All investigated fcc-structured binary alloys are stable under compression. Atomic volumes and bulk moduli show good agreement with ideal solutions model. For fcc–Ir0.50Pt0.50, V0/Z = 14.597(6) Å3·atom−1, B0 = 321(6) GPa and B0’ = 6(1); for fcc–Rh0.66Pt0.33, V0/Z = 14.211(3) Å3·atom−1, B0 =259(1) GPa and B0’ = 6.66(9) and for fcc–Rh0.50Pd0.50, V0/Z = 14.18(2) Å3·atom−1, B0 =223(4) GPa and B0’ = 5.0(3)