Mesoporous poorly crystalline α-Fe2O3 with abundant oxygen vacancies and acid sites for ozone decomposition

Abstract

In this work, mesoporous poorly crystalline hematite (α-Fe₂O₃) was prepared using mesoporous silica (KIT-6) functionalized with 3-[(2-aminoethyl)amino]propyltrimethoxysilane as a hard template (SMPC-α-Fe₂O₃). The disordered atomic arrangement structure of SMPC-α-Fe₂O₃ promoted the formation of oxygen vacancies, which was confirmed using X-ray photoelectron spectroscopy (XPS), O₂-temperature-programmed desorption (TPD), H₂-temperature-programmed reduction (TPR), and in situ diffuse reflectance infrared Fourier transform (DRIFT) analyses. Density functional theory calculations (DFT) also proved that reducing the crystallinity of α-Fe₂O₃ decreased the formation energy of oxygen vacancies. TPD and in situ DRIFT analyses of NH₃ adsorption suggested that the surface acidity of SMPC-α-Fe₂O₃ was considerably higher than those of mesoporous poorly crystalline α-Fe₂O₃ (MPC-α-Fe₂O₃) and highly crystalline α-Fe₂O₃ (HC-α-Fe₂O₃). The oxygen vacancies and acid sites formed on α-Fe₂O₃ surface are beneficial for ozone (O₃) decomposition. Compared with MPC-α-Fe₂O₃ and HC-α-Fe₂O₃, SMPC-α-Fe₂O₃ exhibited a higher removal efficiency for 200-ppm O₃ at a space velocity of 720 L g^-1 h^-1 at 25 ± 2 °C under dry conditions. Additionally, in situ DRIFT and XPS results suggested that the accumulation of peroxide (O₂^2-) and the conversion of O₂^2- to lattice oxygen over the oxygen vacancies caused catalyst deactivation. However, O₂^2- could be desorbed completely by continuous N₂ purging at approximately 350 °C. This study provides significant insights for developing highly active α-Fe₂O₃ catalysts for O₃ decomposition.

Keywords: Mesoporous structure; Oxygen vacancy; Ozone decomposition; Poorly crystalline structure; α-Fe(2)O(3).