Reactivity of Platinum Metal with Organic Radical Anions from Metal to Negative Oxidation States

The reaction of platinum metal with an organic molecular radical anion leads to the formation of iono-metallic phases where Pt exists under negative oxidation states. This puzzling transformation of a “noncorrodible metal” was examined using localized electrochemical techniques in dimethylformamide containing different tetra-alkylammonium salts chosen as test systems. Our experiments demonstrate that the platinum metal is locally reduced as soon as the Pt faces relatively moderate reducing conditions, for example, when the Pt is used as a negative electrode or when the metal is in the presence of a reducing agent such as an organic radical anion. Scanning electrochemical microscopy (SECM) analysis, current−distance curves, and transient mode responses provide detailed descriptions of the reactivity of Pt to form negative oxidation states (the key step is the reaction of the metal with a molecular reducing agent), of the insulating nature of the “reduced” solid phases of the thermodynamics and kinetics conditions of the Pt conversion. The passage from the conductor to insulator states controlled the spatial development of the reaction that always remains in competition with the other “natural” roles of a metallic electrode. Formally, the phenomena can be treated by analogy with the C. Amatore's model previously developed for the mediated reduction of the poly(tetrafluoroethylene). Consequences of this general reactivity of Pt are discussed in view of a wide utilization of this metal in reductive conditions and the possible applications of such processes in the micropatterning of metallic surfaces

In Situ Synchrotron Powder Diffraction Study of Cd Intercalation into Chevrel Phases: Crystal Structure and Kinetic Effect

Chevrel phases are molybdenum chalcogenides of formula M_<i>x</i>Mo₆X₈ (where M is a cation and X is a chalcogen) that present a complex and captivating intercalation chemistry that has drawn the interest of the solid-state chemistry community since their discovery. This property has a huge potential for applied science and device development for energy storage and pollutant removal and detection, but a deeper knowledge of the intercalation processes and chemistry is still necessary. In the present work, the intercalation of Cd²⁺ in aqueous solution has been studied, taking advantage of the complementarity of electrochemical characterization and synchrotron powder diffraction acquired during an in situ combined experiment. During the experiment, industrially adequate electrochemical conditions (room temperature and reduced process time) were applied, allowing a better understanding of the intercalation processes. The intercalated phases obtained by electrochemistry have been characterized ex situ, and for the first time the structures of Cd₂Mo₆X₈ (X = S, Se) have been determined. Unexpectedly, Cd₂Mo₆Se₈ presents a trigonal crystal structure with only cavity 2 occupied, which has not been encountered before for Chevrel phases

Textured Manganite Films Anywhere

New paradigms are required in microelectronics when the transistor is in its downscaling limit and integration of materials presenting functional properties not available in classical silicon is one of the promising alternatives. Here, we demonstrate the possibility to grow La0.67Sr0.33MnO3 (LSMO) functional materials on amorphous substrates with properties close to films grown on single-crystalline substrates using a two-dimensional seed layer. X-ray diffraction and electron backscatter diffraction mapping demonstrate that the Ca2Nb3O10– nanosheet (NS) layer induces epitaxial stabilization of LSMO films with a strong out-of-plane (001) texture, whereas the growth of LSMO films on uncoated glass substrates exhibits a nontextured polycrystalline phase. The magnetic properties of LSMO films deposited on NS are similar to those of the LSMO grown on SrTiO3 single-crystal substrates in the same conditions (which is used as a reference in this work). Moreover, transport measurements take advantages of the texture and polycrystalline properties to induce low-field magnetoresistance at low temperature and also a high value of 40% magnetoresistance from 10 to 300 K, making it interesting for sensor applications. Therefore, the NS seed layer offers new perspectives for the integration of functional materials grown at moderate temperatures on any substrate, which will be the key for the development of oxitronics