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The effects of grain boundary morphology and stoichiometry had been systematically examined to clarify the role of natural grain boundaries in magnetoresistance of magnetite Fe 3͑1−␦͒ O 4 . We found that the excess resistance, caused by presence of the grain boundaries, is negligibly low in stoichiometric polycrystals. Accordingly, there was no grain boundary magnetoresistance detected in dense polycrystals. Moreover, the incorporation of grain boundaries was found to decrease the resistance of polycrystalline samples below the Verwey transition temperature. That was connected to the enhanced conductivity of grain boundaries appearing due to the local suppression of charge ordering. On the other hand, the essential negative magnetoresistance was detected in granular samples, exploring the point contact geometry for intergrain contacts. That magnetoresistance is characterized by large high-field component and appearance over a wide range of oxidation. It has been explained within the model of magnetically inhomogeneous grain boundary with the characteristic magnetic thickness of the order of exchange length. The magnetoresistance effect was connected to the spin-dependent scattering at the transition layers of magnetization formed around hard magnetic defects. The contraction of these transition layers by external magnetic field is supposed to provide the origin of the observed magnetoresistance. The analysis of appropriate microscopic scattering mechanisms reveals the important role of point defects in the spin-dependent scattering. The second magnetoresistance component was separated at highly oxidized grain boundaries and associated with tunneling transport across the isolating grain boundaries. Although the oxidation was shown to improve the isolating properties of natural grain boundaries, the performance of oxidized grain boundary as a tunneling barrier is still poor.

The recently proposed highly efficient route of pyridine-catalyzed CO2 reduction to methanol was explored on platinum electrodes at high CO2 pressure. At 55 bar (5.5 MPa) of CO2 , the bulk electrolysis in both potentiostatic and galvanostatic regimes resulted in methanol production with Faradaic yields of up to 10 % for the first 5-10 C cm(-2) of charge passed. For longer electrolysis, the methanol concentration failed to increase proportionally and was limited to sub-ppm levels irrespective of biasing conditions and pyridine concentration. This limitation cannot be removed by electrode reactivation and/or pre-electrolysis and appears to be an inherent feature of the reduction process. In agreement with bulk electrolysis findings, the CV analysis supported by simulation indicated that hydrogen evolution is still the dominant electrode reaction in pyridine-containing electrolyte solution, even with an excess CO2 concentration in the solution. No prominent contribution from either a direct or coupled CO2 reduction was found. The results obtained suggest that the reduction of CO2 to methanol is a transient process that is largely decoupled from the electrode charge transfer.