Manganites are multifunctional materials which are widely used in both technology and devices. In this article, new prospects of their use as nanoparticles for various types of applications are demonstrated. For that, the ferromagnetic nanopowder of La0.6Sr0.4MnO3 has been synthesized by the sol–gel method with a subsequent annealing at 700–900 °C. The crystal structure, phase composition and morphology of nanoparticles as well as magnetic, magnetothermal and electrocatalytic properties have been studied comprehensively. The critical sizes of superparamagnetic, single-domain, and multi-domain states have been determined. It has been established that an anomalously wide temperature range of magnetocaloric properties is associated with an additional contribution to the magnetocaloric effect from superparamagnetic nanoparticles. The maximum values of the specific loss power are observed in the relaxation hysteresis region near the magnetic phase transition temperature. The electrochemical stability and features of the decomposition of nanoparticles in 1 M KOH and Na2SO4 electrolytes have been determined. A decrease in the particle size contributes to an increase in electrocatalytic activity for overall water splitting. Magnetocaloric and electrocatalytic results of the work indicate the prospects for obtaining the possibility of changing the temperature regime of electrocatalysis using contactless heating or cooling.
Ceramic samples of lanthanum strontium manganite perovskites La0.6Sr0.2Mn1.2 − xNixO3 ± δ (0 ≤ x ≤ 0.3) have been investigated using the X-ray diffraction, magnetic (χac), 55Mn NMR, resistive, and magnetoresistive methods. The specific features of the influence of the composition on the structure and properties of nonstoichiometric manganite perovskites have been established. It has been found that the rhombohedrally (R $\bar 3$ c) distorted perovskite structure contains cation and anion vacancies, as well as nanostructured clusters with Mn2+ ions in the A-positions. The substitution of Ni3+ ions (r = 0.74 Å) for Mn3+ ions (r = 0.785 Å) leads to a decrease in the lattice parameter a, the ferromagnetic-paramagnetic phase transition temperature TC, and the metal-semiconductor phase transition temperature Tms due to the disturbance of the superexchange interactions between heterovalent manganese ions Mn3+ and Mn4+. The observed anomalous magnetic hysteresis at 77 K has been explained by the antiferromagnetic effect of the unidirectional exchange anisotropy of the ferromagnetic matrix structure on the magnetic moments of the superstoichiometric manganese Mn2+ ions located in nanostructured planar clusters. An analysis of the asymmetrically broadened 55Mn NMR spectra of the compounds has revealed a high-frequency electronic superexchange of the ions Mn3+ ⟷ O2− ⟷ Mn4+; a local heterogeneity of their surrounding by other ions, vacancies, and clusters; and a partial localization of Mn4+ ions. The local hyperfine interaction fields on 55Mn nuclei have been determined. The concentration dependences of the activation energy and charge hopping frequency have confirmed that the Ni ions decrease the electrical conductivity due to the weakening of the electronic superexchange Mn3+ ⟷ O2− ⟷ Mn4+. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures TC and Tms, is caused by scattering at intracrystalline nanostructured heterogeneities, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between magnetic and electrical properties in rare-earth manganites.