Influence of pH and Fe doping on structural and physical properties of Mg0.95Mn0.05-Fe O (x = 0, 0.04) nanoparticles

Abstract We investigate the effects of pH and Fe doping on the size, structural and physical properties of Mg 0.95 Mn 0.05- x Fe x O ( x  = 0, 0.04) nanoparticles. All the nanoparticles were synthesized by the sol-gel autocombustion method by varying the pH of the solution. Furthermore, the phase purity, size, and size distribution of the nanoparticles were studied by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Irrespective of the pH, Rietveld refinement analysis of the XRD data reveals single crystallographic cubic phases with MgO-type wurtzite structure (space group F m 3 ¯ m ) along with a lattice parameter of 4.2121(8) A for x  = 0.0 and 4.2083(5) A for x =  0.04. This change in lattice parameter with Fe doping is due to the smaller size of Fe 2+ (78 p.m.) compared with Mn 2+ (83 p.m.). The size of the nanoparticles increases monotonically from approximately 10 nm to approximately 16 nm for x  = 0.0 and from approximately 18 nm to approximately 23 nm for x  = 0.04 with increasing pH. SEM micrographs of the powders show highly agglomerated nanoparticles with porous and irregular morphology. The TEM findings support the XRD results, showing that the nanoparticles increase in size with increase in pH. Because Raman modes should be absent in bulk MgO and present in MgO nanoparticles, the strong intensity of the three Raman modes at approximately 380 cm −1 , 470 cm −1 , and 608 cm −1 further supports the formation of small nanoparticles of Mg 0.95 Mn 0.05- x Fe x O ( x  = 0, 0.04). The decrease in peak intensity with increase in pH suggests an increase in the size of the nanoparticles. The peak at 470 cm −1 corresponds to a transverse optical phonon, while the peak at 380 cm −1 corresponds to a transverse acoustic phonon.