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.

Aluminothermic Synthesis of Dispersed Electrides Based on Mayenite: XRD and EPR Study.

The evolution of the structure and the phase composition of a dispersed mayenite at its interaction with metallic aluminum was studied in a temperature range from 900 to 1400 °C in both argon and air atmospheres. The aluminum loading was varied from 0 to 50 wt%. It was found that the addition of aluminum significantly affects the stability of the mayenite and other calcium aluminate phases within the studied temperature range. The formation of the electride state registered by the appearance of a characteristic electron paramagnetic resonance (EPR) signal from F+-like centers (g~1.994) in an argon atmosphere was shown to take place already at 1150 °C due to an aluminothermic reduction of this material. The super-narrow (Hp-p < 0.5 G) EPR spectra from F+-like centers, which were recently observed for the core−shell structures of the C12A7@C type only, were registered for mayenite for the first time. The results obtained in the present study testify firstly towards the possibility of significantly diminishing the temperatures required for the formation of the electride state in such systems and secondly towards the ability to stabilize the size of small electride nanoparticles within the synthesized calcium aluminate matrix.

Comparative Study on Carbon Erosion of Nickel Alloys in the Presence of Organic Compounds under Various Reaction Conditions.

The processes of carbon erosion of nickel alloys during the catalytic pyrolysis of organic compounds with the formation of carbon nanofibers in a flow-through reactor as well as under reaction conditions in a close volume (Reactions under Autogenic Pressure at Elevated Temperature, RAPET) were studied. The efficiency of the ferromagnetic resonance method to monitor the appearance of catalytically active nickel particles in these processes has been shown. As found, the interaction of bulk Ni-Cr alloy with the reaction medium containing halogenated hydrocarbons (1,2-dichloroethane, 1-iodobutane, 1-bromobutane) results in the appearance of ferromagnetic particles of similar dimensions (~200-300 nm). In the cases of hexachlorobenzene and hexafluorobenzene, the presence of a hydrogen source (hexamethylbenzene) in the reaction mixture was shown to be highly required. The microdispersed samples of Ni-Cu and Ni-Mo alloys were prepared by mechanochemical alloying of powders and by reductive thermolysis of salts-precursors, accordingly. Their interaction with polymers (polyethylene and polyvinyl chloride) under RAPET conditions and with ethylene and 1,2-dichloroethane in a flow-through reactor are comparatively studied as well. According to microscopic data, the morphology of the formed carbon nanofibers is affected by the alloy composition and by the nature of the used organic substrate.

Resistance Switching in Polycrystalline C12A7 Electride.

The memory (memristive) properties of an electride material based on polycrystalline mayenite (C12A7:e-) were studied. The phase composition of the material has been confirmed by such methods as XRD, TEM, Raman, and infrared spectroscopy. The electride state was confirmed by conductivity measurements and EPR using a characteristic signal from F+-like centers, but the peak at 186 cm-1, corresponding to an electride with free electrons, was not observed explicitly in the Raman spectra. The temperature dependence of current-voltage characteristics in states with low and high resistance (LRS and HRS) has been studied. In the LRS state, the temperature dependence of the current has a non-Arrhenius character and is described by the Hurd quantum tunnelling model with a Berthelot temperature of 262 K, while in the HRS state, it can be described in terms of the Arrhenius model. In the latter case, the existence of two conduction regions, "impurity" and "intrinsic", with corresponding activation energies of 25.5 and 40.6 meV, was assumed. The difference in conduction mechanisms is most likely associated with a change in the concentration of free electrons.

Mayenite Synthesis from Hydroxide Precursors: Structure Formation and Active Sites on Its Surface.

We studied the formation process of a mayenite structure from hydroxide precursors in different gas media. According to X-ray diffraction data, this method allows a well-crystallized mayenite (Ca12Al14O33 or C12A7) phase to be obtained at low (500-900 °C) temperatures with an insignificant impurity of CaO. It was shown that the lattice parameters for C12A7 obtained in an inert atmosphere (Ar) were lower when compared with similar samples in the air. These results can be explained by the different levels of oxygen nonstoichiometry in the resulting phase. We noted that sintering and crystallization of mayenite proceeds at lower temperatures in Ar than in the air medium. We found the presence of donor and acceptor active sites on the surface of mayenite, which was detected by the spin probe method. The specific (per unit surface) concentration of such sites (2.5 × 1016 m-2 and 1.5 × 1015 m-2 for donor and acceptor sites, respectively) is comparable to that of γ-Al2O3, which is traditionally used as catalyst support. This allows it to be used in adsorption and catalytic technologies, taking into account its high specific surface area (~30-50 m2/g at a low synthesis temperature).

CO Oxidation over Pd/ZrO2 Catalysts: Role of Support's Donor Sites.

A series of supported Pd/ZrO2 catalysts with Pd loading from 0.2 to 2 wt % was synthesized. The ZrO2 material prepared by a similar technique was used as a reference sample. The samples have been characterized by means of transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), testing reaction of ethane hydrogenolysis (HGE), N2 adsorption, and electron paramagnetic resonance (EPR) spectroscopy. 1,3,5-trinitrobenzene was used as a probe molecule for the EPR spin probe method. The catalytic performance of samples was tested in the model reaction of CO oxidation. It was shown that the concentration of donor sites of support measured by EPR spin probe correlates with catalytic behavior during light-off tests. Low concentration of donor sites on a support's surface was found to be caused by the presence of the specific surface defects that are related to existence of coordinately unsaturated structures.

Characterization of electron donor sites on Al2O3 surface.

Formation of radical anions after adsorption of 1,3,5-trinitrobenzene (TNB) on electron donor sites of fully oxidized Al(2)O(3) samples with different phase compositions is studied by EPR. It is shown that the maximum concentration of the radical anions does not substantially depend on the choice of solvent and reaction temperature, and can be used to measure the total concentration of the donor sites. The donor sites are observed in almost the same concentration about 5 × 10(16) m(-2) on all alumina polymorphs except for α-Al(2)O(3). The formation rate of the TNB radical anions and the activation energy of this process are found to depend on the donor properties of the solvent. The EPR in situ experiments showed that a substantial amount of the adsorbate forming a liquid phase is required for generation of the radical anions. These results prove that the sites measured by the formation of the TNB radical anions are not genuine electron donor sites capable of direct electron transfer to the adsorbed TNB molecules. A model of the observed paramagnetic species based on the obtained experimental data and the results of quantum chemical simulations is suggested. According to this model, a TNB radical anion substitutes a hydroxyl group forming a neutral ion pair with a surface aluminum cation. The suggested mechanism for the formation of such ion pairs involves the migration of simple radicals and does not require long-distance charge separation. It is supposed that the donor site where the process is initiated includes a negatively charged surface hydroxyl group.

Superoxide radical anions on the surface of zirconia and sulfated zirconia: formation mechanisms, properties and structure.

In situ ESR spectroscopy has been used for direct comparison of different thermal and light-induced processes leading to generation of superoxide radical anions on the surface of various zirconia and sulfated zirconia materials. For materials of both types the magnetic resonance parameters of the radical anions were found to be practically independent of the generation method, except for oxygen coadsorption with NO that yields radicals with somewhat smaller gz values. The parameters appear to depend mostly on the state of the surface zirconia cations stabilizing the radical anions, so that the g tensor anisotropy is significantly smaller over sulfated zirconia. It is shown that light-induced formation of superoxide radical anions in the presence of coadsorbed hydrocarbons can be initiated with visible light. Original SIET reaction mechanisms are suggested for the formation of superoxide radical anions by coadsorption with hydrocarbons and illumination after such coadsorption to extend the previously known ones to account for the observed phenomena. Cluster model DFT calculations of magnetic resonance parameters of O2- radical anions stabilized on the surface of zirconium dioxide showed that the adsorption complexes have a -shape rather than linear structure. The magnetic resonance parameters obtained by calculations practically match experimental data and adequately describe their changes after the surface modification with sulfates.

CF2Cl2 decomposition over nanocrystalline MgO: evidence for long induction periods.

CF(2)Cl(2) has been found to react with nanoscale MgO at 325 degrees C and higher temperatures. In excess of the halocarbon, the reaction results in the formation of MgF(2) as a predominant solid product, with CCl(4), and CO(2) formed as the main gaseous products. The kinetics of the process is characterized by a prolonged induction period, which is as long as 8.5 h at 325 degrees C. The length of the induction period decreases with temperature increase and becomes negligible at 500 degrees C. Complete CF(2)Cl(2) mineralization has been achieved in an excess of MgO at 450 degrees C. Detailed HRTEM and EDX analysis has shown that the induction period involves the formation of small amounts of magnesium halides on the oxide surface and results in its reconstruction leading to initial oriental ordering of the nanocrystals followed by substantial changes in the bulk composition of the nanoparticles. The reaction proved to be structurally sensitive. It has been found that deep fluoridation is possible only for nanoscale MgO samples. The use of samples with lower surface areas results in lengthening of the induction period and decrease of the reaction depth. The MgO transformation to MgF(2) has been found to result in a surface area decrease by more that an order of magnitude as a result of intense sintering of magnesium fluoride under the reaction conditions.