Rare-earth-based ternary compounds with the formula REBO4 (B = V, Cr, P, As) exhibit rich structural chemistry and associated technologically significant properties. Among the rare-earth chromates, realizing PrCrO4 in a single polymorphic modification has been challenging. Herein, we report the successful stabilization of the zircon polymorph of PrCrO4 by introducing 10 mol % of VO43- instead of CrO43- following a solution combustion method. Compositions with progressively higher amounts of vanadate have been synthesized and characterized extensively. XPS analysis of 10 and 50 mol % VO43- substituted PrCrO4 samples ascertained the existence of Pr3+/4+, Cr4+,5+, and V5+ in them, making it a red-ox-rich system. The tetragonal symmetry of PrCr0.50V0.50O4 was confirmed from the HRTEM images and SAED patterns. FTIR and Raman spectral analyses indicated distorted tetrahedral (Cr/VO4) units with a local site symmetry below D2d. Both d-d and f-f transitions of Cr4+ and Pr3+, respectively, were observed in the absorption spectra. Field and temperature-dependent magnetic measurements of PrCr0.50V0.50O4 confirmed its predominant paramagnetic behavior. The samples possessed porous morphology with a reasonable surface area. PrCr1-xVxO4 (x = 0.00-0.50) samples catalyzed the oxidation of phenol. This study demonstrated B-site tuning in ABO4 systems to select a desired polymorph preferentially.
Read full abstract