Electronic properties and native point defects of high efficient NO oxidation catalysts SmMn2O5

Abstract

Mn-based oxide SmMn2O5 exhibits great catalytic performance in NO oxidation [Wang et al., Science 337, 832 (2012)]. Nevertheless, the fundamental understanding of SmMn2O5 properties is so far not fully accessible. Here, the SmMn2O5 nanoparticles are synthesized through hydrothermal methods, and the pure phase of triclinic SmMn2O5 is characterized by high-resolution tunneling electron microscope and X-ray diffraction. Furthermore, the X-ray photoelectron spectroscopy, absorption, photoluminescence spectra (PL), and density functional theory based first-principles calculations are employed to explore the fundamental electronic structures of pristine and defective SmMn2O5. Combined with band structure calculations, light absorption, and PL spectra, we first show that SmMn2O5 presents an insulating behavior with an indirect band gap of ∼1.0 eV. Between the two types of crystal fields, i.e., octahedral and tetrahedral, the later one contributes to the dz2 of the valence band edge, resulting in superior catalytic performance of NO oxidation. Furthermore, the native point defects in SmMn2O5 are first reported. Among the various native point defects, we demonstrate that oxygen vacancy (VO) shows the lowest formation energy in oxygen poor conditions, while the oxygen interstitial (Oi) and Mn vacancies are energetically favorable in oxygen rich situations. In other words, SmMn2O5 could be potentially utilized as an oxygen storage material.