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Nowadays, Ni@C nanostructured materials are attracting a great deal of attention due to their multiple catalytic or magnetic functionalities. In this article we report on the investigation of the correlation between the microstructure and magnetic properties of Ni nanoparticles embedded in a carbon matrix. The samples were obtained following a two-step procedure that ensures protection against nanoparticle oxidation, and was carried out in the following way: (i) the synthesis of a nickel-imidazole-based metal-organic framework (MOF) by a simple method in an aqueous medium at moderate temperature (95 °C); and (ii) carbonization of the MOF at different temperatures between 400 and 600 °C to obtain a carbon-supported hybrid material, containing Ni nanoparticles with an “artichoke-like” morphology, where a Ni-FCC core is surrounded by “bracts” of Ni-HCP and Ni3C. The average size of the nanoparticle slightly changes from 7 to 10 nm as the carbonization temperature is increased, but the Ni-FCC core diameter ranges from 3 to around 6 nm. We show how the information obtained on the evolution of the magnetic behaviour with carbonization temperature, using X-ray diffraction and electron microscopy, complements each other by providing consistent structural and magnetic characteristics of the investigated Ni@C nanoparticles. In fact, this joint analysis allows us to explain the formation and transformation of different Ni-based crystalline phases along the synthesis process, including Ni3C and Ni with both hexagonal and cubic crystalline structures. The amount of conventional Ni-FCC is below 10 wt% for the sample treated at 400 °C and it can reach up to 50 wt% for that treated at 600 °C. Finally, based on our current findings we propose an explanation for understanding the magnetic properties of Ni@C, in which the Ni-FCC core spins mainly govern the magnetic coupling of the whole system.

Bulk Cr2O3 is an antiferromagnetic (AFM) oxide that exhibits the magnetoelectric effect at room temperature, with neither spontaneous magnetization nor net electric polarization. These physical properties stem from a subtle competition between exchange and crystal field interactions. In this article, we exploit the symmetry breaking at the surface of Cr2O3 nanoparticles for unbalancing this delicate physical equilibrium. The emerging weak ferromagnetic signal we observe persists up to near room temperature (≈ 270 K) at which the antiferromagnetic order disappears. In addition, an exchange-bias effect, that rapidly decreases on heating from low temperature up to 30 K, is resistant to thermal disorder above 200 K. Our findings point to the possible formation of an entangled core/shell magnetic structure, where pinned uncompensated spins at the shell are randomly distributed in a low-temperature spin-glass ordering, with low net magnetic moment and an ordering temperature governed by the AFM Néel temperature.

The control of chemical, morphological, textural and magnetic properties developed in magnetic activated carbons (MACs) from industrial food waste, was achieved. The process parameters involved in a sustainable and optimized one-step activation route, based on the circular economy model, played an important role and its influence was studied, offering interesting and outstanding results. Magnetite crystals were formed on the MACs surface obtained from 400 °C to 800 °C while other iron species, such as metallic iron and iron carbides, were formed only at 800° C. Acid washing favored the mineral matter removal and the presence of iron species was drastically reduced in acid-washed MACs, mainly the iron species originated at 800 °C. Water-washed MACs presented better magnetic response at high temperatures (confirmed by XRD, FTIR, Raman, Mössbauer spectroscopy and VSM characterization techniques). High BET surface area (≈ 822 m/g) and a large micropore volume (≈ 0.30 cm/g), were reached by acid washed MACs at 800 °C. The obtained MACs were fundamentally microporous, but some mesoporosity was also observed when activating agent/precursor mass ratio (1:1) is used. It can be concluded that a MACs strategic design was reached with the objective of removing specific pollutants in multiple environmental applications.

NiO nanoparticles (NPs) with a nominal size range of 2–10 nm, synthesized via hightemperature pyrolysis of a nickel nitrate, have been extensively investigated using neutron diffraction and magnetic (ac and dc) measurements. The magnetic behavior of the NPs changes noticeably when their diameter decreases below 4 nm. For NPs larger than or equal to this size, Rietveld analysis of the room temperature neutron diffraction patterns reveals that there is a reduction in the expected magnetic moment per Ni2+ ion with respect to bulk NiO, which is linked to the existence of a magnetically disordered shell at the NP surface. The presence of two peaks in the temperature dependence of both the dc magnetization after zero-field-cooling and the real part of the ac magnetic susceptibility is explained in terms of a core (antiferromagnetic, AFM)/shell (spin glass, SG) morphology. The high-temperature peak (T > 50 K) is associated with collective blocking of the uncompensated magnetic moments inside the AFM core. The low-temperature peak (T < 10 K) is a signature of a SG-like freezing of the surface Ni2+ spins. In addition, an exchange bias (EB) effect emerges due to the core/shell magnetic coupling. The cooling field and temperature dependences of the EB effect and the coercive field are discussed in terms of the core size and the effective magnetic anisotropy of the NPs. However, NiO NPs of 2 nm in size no longer show AFM order and the Ni2+ magnetic moments freeze into a SG-like state below T ∼ 3 K, with no evidence of EB effect.

We have studied the correlation between the broadening of the isothermal magnetic entropy change and the Curie temperature (TC) distribution in nanostructured Pr2Fe17 and Nd2Fe17 alloys produced by high-energy ball-milling after milling times of 10, 20, and 40 h. The changes in the microstructure affect the Fe local environments and as a consequence the magnetic interactions, giving rise to TC distributions centered around 285 K and 330 K for the Pr2Fe17 and Nd2Fe17 alloys, respectively. The width of the distributions enlarges (up to 60 K) as the milling-time increases, and consequently, the isothermal magnetic entropy change curves show an extended full width at half maximum.

Several pseudo-binary RxR'2-xFe17 alloys (with R = Y, Ce, Pr, Gd and Dy) were synthesized with rhombohedral Th2Zn17-type crystal structure determined from x-ray and neutron powder diffraction. The choice of compositions was done with the aim of tuning the Curie temperature (TC) in the 270 ± 20 K temperature range, in order to obtain the maximum magneto-caloric effect around room temperature. The investigated compounds exhibit broad isothermal magnetic entropy changes, ΔSM(T), with moderate values of the refrigerant capacity, even though the values of ΔSMPeak are relatively low compared with those of the R2Fe17 compounds with R = Pr or Nd. The reduction on the ΔSMPeak is explained in terms of the diminution in the saturation magnetization value. Furthermore, the ΔSM(T) curves exhibit a similar caret-like behavior, suggesting that the magneto-caloric effect is mainly governed by the Fe-sublattice. A single master curve for ΔSM/ΔSMPeak(T) under different values of the magnetic field change are obtained for each compound by rescaling of the temperature axis.

Several pseudo-binary RxR2-x'Fe-17 alloys (with R = Y, Ce, Pr, Gd and Dy) were synthesized with rhombohedral Th2Zn17-type crystal structure determined from x-ray and neutron powder diffraction. The choice of compositions was done with the aim of tuning the Curie temperature (T-C) in the 270 +/- 20 K temperature range, in order to obtain the maximum magneto-caloric effect around room temperature. The investigated compounds exhibit broad isothermal magnetic entropy changes, Delta S-M(T), with moderate values of the refrigerant capacity, even though the values of Delta S-M(Peak) are relatively low compared with those of the R2Fe17 compounds with R = Pr or Nd. The reduction on the Delta S-M(Peak) is explained in terms of the diminution in the saturation magnetization value. Furthermore, the Delta S-M(T) curves exhibit a similar caret-like behavior, suggesting that the magneto-caloric effect is mainly governed by the Fe-sublattice. A single master curve for Delta S-M/Delta S-M(Peak)(T) under different values of the magnetic field change are obtained for each compound by rescaling of the temperature axis.