Structure dependent luminescence, peroxidase mimetic and hydrogen peroxide sensing of samarium doped cerium phosphate nanorods

Abstract

Rare earth phosphates have been used extensively in luminescent phosphors, bio-imaging, catalysis, and sensors. However, there is a need to correlate the structural-chemical changes associated with stability and performance. In the present work, hydrothermally synthesized CePO₄:Sm_x (x = 0, 5 and 10 mol%) nanorods were annealed at different temperatures to understand the modulations in structure as well as optical and enzyme mimetic properties. As prepared samarium doped cerium phosphate (SCP) nanorods crystallized in a hydrated hexagonal structure transformed into an anhydrous hexagonal and a monoclinic structure on annealing at 400 °C and 800 °C, respectively. Though temperature did not affect the rod-like morphology of the SCP, the lattice strain changed from compressive to tensile. Monoclinic SCP exhibited excellent emission until 5% Sm³⁺ doping while the quenching effect dominated at 10% Sm³⁺. Monoclinic SCP samples demonstrated higher peroxidase-like enzymatic activity in comparison to natural enzyme HRP and hexagonal SCP. A mechanism for the enhanced peroxidase-like activity of the monoclinic structure was proposed based on the fluorescence property of terephthalic acid and the surface peroxo complex using Raman spectroscopy. Fluorimetric detection based on the luminescent quenching effect of the monoclinic SCP nanorods treated with different concentrations of hydrogen peroxide showed a linear response from 0 to150 μM concentration with a detection limit (LOD) of 3.17 μM H₂O₂. Our results demonstrate the importance of structure for enzyme mimetic activity.