Unlocking the chemical environment of nitrogen in perovskite-type oxides

Abstract

Nitrogen (N) doping of perovskite-type oxides is an effective method for enhancing their photocatalytic performance. Quantitative and qualitative analyses of the doped N species are essential for a deeper understanding of the catalytic activity enhancement mechanism. However, examining the N environment in perovskite-type oxides, particularly in the bulk, using conventional analytical techniques, such as X-ray photoelectron spectroscopy (XPS), is challenging. In this study, we propose a new analytical technique, advanced temperature-programmed desorption (TPD) up to 1600 °C, to complement the conventional methods. TPD can quantify all N species in bulk oxides. Moreover, it facilitates chemical speciation of N environments, such as substitutional and interstitial N species. This is verified by XPS, CHN elemental analysis, X-ray absorption spectroscopy, and in situ diffuse reflectance infrared Fourier-transform spectroscopy. This study demonstrates the feasibility of advanced TPD as a new analytical method that offers comprehensive information on the N species within N-doped oxide materials at the bulk level.