Our study is focused on the structural and morphological characteristics, optical behaviour and photocatalytic properties of undoped and 5 at% Eu³⁺-, Gd³⁺- and Y³⁺-doped CeO₂ nanoparticles prepared by a green hybrid sol-gel combustion method. Several techniques such as X-ray diffraction powder (XRD), Transmission Electron Microscopy (TEM), UV-Vis spectroscopy, Photoluminescence spectroscopy (PL) and Electron Paramagnetic Resonance (EPR) have been used to investigate the obtained samples. Moreover, the correlation between the characteristics and properties has been studied. The nanoparticles observed by TEM exhibit a pseudo-spherical shape, except for Y³⁺-doped CeO₂, which presents an acicular shape. The average size of undoped and rare-earth-doped CeO₂ nanoparticles is below 10 nm, in good agreement with the calculations performed based on XRD analyses. From UV-Vis analyses it has been deduced that with doping the band gap energy decreases, which shows that additional levels are introduced by doping into the CeO₂ band gap. The EPR spectra evidence similar behaviour for all doped samples. The photocatalytic activity was evaluated by the degradation of rhodamine B (RhB) under UV light irradiation. The photodegradation mechanism has been studied in depth based on the formation of electron-hole pairs, and to evidence the reactive oxygen species, ESR coupled with spin-trapping experiments was performed. In the case of Y-doped CeO₂ nanoparticles, the generation of both •OOH and •${\mathrm{O}}_2^{-}$ radicals involved in RhB photodegradation was highlighted.

Co_1−xZn_xFe₂O₄ nanoparticles (0 ≤ x ≤ 1) have been synthesized via a green sol–gel combustion method. The prepared samples were studied using X-ray diffraction measurements (XRD), transmission electron microscopy (TEM), Raman, and magnetic measurements. All samples were found to be single phases and have a cubic Fd-3m structure. EDS analysis confirmed the presence of cobalt, zinc, iron, and oxygen in all studied samples. Raman spectra clearly show that Zn ions are preferentially located in T sites for low Zn concentrations. Due to their high crystallinity, the nanoparticles show high values of the magnetization, which increases with the Zn content for x < 0.5. The magnetic properties are discussed based on Raman results. Co ferrite doped with 30% of Zn produced the largest SAR values, which increase linearly from 148 to 840 W/g_MNPs as the H is increased from 20 to 60 kA/m.

Co_0.95R_0.05Fe₂O₄ nanoparticles with R = La, Pr, Nd, Sm, and Eu were synthesized via an environmentally friendly sol–gel method. The prepared samples were studied using X-ray diffraction measurements (XRD), transmission electron microscopy (TEM), X-ray photoelectron microscopy (XPS), and magnetic measurements. All compounds were found to be single phases adopting a cubic Fd-3m structure. EDS analysis confirmed the presence of Co, Fe, R, and oxygen in all cases. The XPS measurements reveal that the Co 2p core-level spectra are characteristic for Co³⁺ ions, as indicated by the 2p_3/2 and 2p_1/2 binding energies and spin–orbit splitting values. The analysis of the Fe 2p core-level spectra reveals the presence of both Fe³⁺ and Fe²⁺ ions in the investigated samples. The doped samples exhibit lower saturation magnetizations than the pristine sample. Very good agreement with the saturation magnetization values was obtained if we assumed that the light rare-earth ions occupy octahedral sites and their magnetic moments align parallel to those of the 3d transition metal ions. The ZFC-FC curves indicate that some nanoparticles remain superparamagnetic, while others exhibit ferrimagnetic ordering at room temperature, suggesting the presence of interparticle interactions. The M_r/M_s ratio at room temperature reflects the dominance of magnetostatic interactions.

Here, we report synthesis and investigations of bulk and nano-sized La_(0.7−x)Eu_xBa_0.3MnO₃ (x ≤ 0.4) compounds. The study presents a comparison between the structural and magnetic properties of the nano- and polycrystalline manganites La_(0.7−x)Eu_xBa_0.3MnO₃, which are potential magnetocaloric materials to be used in domestic magnetic refrigeration close to room temperature. The parent compound, La_0.7Ba_0.3MnO₃, has Curie temperature T_C = 340 K. The magnetocaloric effect is at its maximum around T_C. To reduce this temperature below 300 K, we partially replaced the La ions with Eu ions. A solid-state reaction was used to prepare bulk polycrystalline materials, and a sol-gel method was used for the nanoparticles. X-ray diffraction was used for the structural characterization of the compounds. Transmission electron spectroscopy (TEM) evidenced nanoparticle sizes in the range of 40–80 nm. Iodometry and inductively coupled plasma optical emission spectrometry (ICP-OES) was used to investigate the oxygen content of the studied compounds. Critical exponents were calculated for all samples, with bulk samples being governed by tricritical mean field model and nanocrystalline samples governed by the 3D Heisenberg model. The bulk sample with x = 0.05 shows room temperature phase transition T_C = 297 K, which decreases with increasing x for the other samples. All nano-sized compounds show lower T_C values compared to the same bulk samples. The magnetocaloric effect in bulk samples revealed a greater magnetic entropy change in a relatively narrow temperature range, while nanoparticles show lower values, but in a temperature range several times larger. The relative cooling power for bulk and nano-sized samples exhibit approximately equal values for the same substitution level, and this fact can substantially contribute to applications in magnetic refrigeration near room temperature. By combining the magnetic properties of the nano- and polycrystalline manganites, better magnetocaloric materials can be obtained.

Here we report investigations of bulk and nano-sized Pr_0.65Sr_(0.35−x)Ca_xMnO₃ compounds (x ≤ 0.3). Solid-state reaction was implemented for polycrystalline compounds and a modified sol–gel method was used for nanocrystalline compounds. X-ray diffraction disclosed diminishing cell volume with increasing Ca substitution in Pbnm space group for all samples. Optical microscopy was used for bulk surface morphology and transmission electron microscopy was utilized for nano-sized samples. Iodometric titration showed oxygen deficiency for bulk compounds and oxygen excess for nano-sized particles. Measurements of resistivity of bulk samples revealed features at temperatures associated with grain boundary condition and with ferromagnetic (FM)/paramagnetic (PM) transition. All samples exhibited negative magnetoresistivity. Magnetic critical behavior analysis suggested the polycrystalline samples are governed by a tricritical mean field model while nanocrystalline samples are governed by a mean field model. Curie temperatures values lower with increasing Ca substitution from 295 K for the parent compound to 201 K for x = 0.2. Bulk compounds exhibit high entropy change, with the highest value of 9.21 J/kgK for x = 0.2. Magnetocaloric effect and the possibility of tuning the Curie temperature by Ca substitution of Sr make the investigated bulk polycrystalline compounds promising for application in magnetic refrigeration. Nano-sized samples possess wider effective entropy change temperature (ΔT_fwhm) and lower entropy changes of around 4 J/kgK which, however, puts in doubt their straightforward potential for applications as magnetocaloric materials.

We report the successful synthesis and a complete magnetic characterization of CoFe₂O₄@SiO₂@Au magnetoplasmonic nanoparticles. The CoFe₂O₄ magnetic nanoparticles were prepared using the hydrothermal method. A subsequent SiO₂ shell followed by a plasmonic Au shell were deposited on the magnetic core creating magnetoplasmonic nanoparticles with a core–shell architecture. A spin-glass-type magnetism was shown at the surface of the CoFe₂O₄ nanograins. Depending on the external magnetic field, two types of spin-glass were identified and analyzed in correlation with the exchange field acting on octahedral and tetrahedral iron sites. The magnetization per formula unit of the CoFe₂O₄ core is not changed in the case of CoFe₂O₄@SiO₂@Au nanocomposites. The gold nanoparticles creating the plasmonic shell show a giant diamagnetic susceptibility, dependent on their crystallite sizes.