Green Synthesis of Nd-Doped ZnO Powders via Freeze-Drying and Hydrothermal Processes

Green-synthesized Nd-doped (2%)-ZnO samples were produced using hydrothermal synthesis (HT) and freeze-drying (FT) procedures. A water extract from Vaccinium vitis-idaea leaves was used to modify the Nd-containing zinc acetate solution. The hydrothermal synthesis was carried out in an autoclave at 170 °C for 8 h. The lyophilization process was carried out for 20 h at 0.15 mbar and then for a further 4 h at 0.10 mbar and at a temperature of −100 °C. The final treatment after both these procedures was carried out at 400 °C for 2 h. Both synthesis methods produced mixtures of rugby-like and ridged ZnO particles. The FT particles possess smaller crystallites sizes (24 nm) and higher polarity (I002/I100) in comparison with the hydrothermally obtained particles. It was ascertained by EPR analyses that there was a higher concentration of oxygen-vacancies-related paramagnetic centers after freeze-drying synthesis (more intensive line at g = 2.000). The photocatalytic reaction rates of the freeze-dried samples toward Malachite Green dye discoloration were found to be higher than those of the HT samples. These rates were greatly affected by the smaller crystallites sizes, higher number of singly ionized oxygen vacancies in the crystal lattice and higher surface polarity.