Exsolved perovskites can be obtained from lanthanum ferrites, such as La0.6Sr0.4Fe0.8Co0.2O3, as result of Ni doping and thermal treatments. Ni can be simply added to the perovskite by an incipient wetness method. Thermal treatments include calcination in air (e.g., 500 °C) and subsequent reduction in diluted H2 at 800 °C to favor the exsolution process. The chemistry of the nanoparticles exsoluted on the substrate surface can be further modulated by a post treatment in air. These processes allow to produce a two-phase material consisting of a Ruddlesden-Popper type structure and a solid oxide solution e.g. α-Fe100-y-zCoyNizOx oxide. The formed electro-catalyst shows sufficient electronic conductivity under reducing environment at the SOFC anode. Outstanding catalytic properties are observed for the direct oxidation of dry fuels in SOFCs, including H2, methane, syngas, methanol, glycerol and propane. This anode electrocatalyst can be combined with full density electrolyte based on Gadolinia-doped Ceria or with La0.8Sr0.2Ga0.8Mg0.2O3 (LSGM) or BaCe0.9Y0.1O3-δ (BYCO) to form a complete perovskite structure-based cell. Moreover, the exsolved perovskite can be used as a coating layer or catalytic pre-layer of a conventional Ni-YSZ anode. Beside the excellent catalytic activity, this material also shows proper durability and tolerance to sulphur poisoning. In this mini review, preparation methods, physico-chemical characteristics, surface properties of exsoluted and core-shell nanoparticles encapsulated on the metal-depleted perovskite substrate surface, electrochemical properties for the direct oxidation of dry fuels and related electrooxidation mechanisms are examined and discussed.

The co-electrolysis of CO2 and H2O at intermediate temperature is a viable approach for the power-to-gas conversion that deserves for further investigation, considering the need for green energy storage. The commercial solid oxide electrolyser is a promising device, but it is still facing to solve issues concerning the high operating temperatures and the improvement of gas value. In this paper we reported the recent findings of a simple approach that we have amply suggested for solid oxide cells consisting in the addition of a functional layer coated to the fuel electrode of commercial electrochemical cells. This approach simplifies the transition to the next generation of cells manufactured with the most promising materials currently developed and improves the gas value in the outlet stream of cell. Here, the material in use as a coating layer consisted of a Ni-modified La0.6Sr0.4Fe0.8Co0.2O3 which was developed and demonstrated as promising fuel electrode for solid oxide fuel cells. The results discussed in this paper proved the positive role of Ni-modified perovskite as a coating layer for the cathode, since an improvement of about twice was obtained about the quality of gas produced.