Density Functional Theory Evaluation of Ceramics Suitable for Hybrid Advanced Oxidation Processes: A Case Study for Ce⁴⁺-Doped BaZrO₃

Abstract

Ceramic photocatalysts have become a focus of several research works in the sonochemistry community owing to their potential for enhancing the degradation of organic pollutants during sonocatalysis or sonophotocatalysis. Although various ceramic materials have been developed and employed in hybrid advanced oxidation processes in the past decades, the physics and chemistry governing the photocatalytic performance of these materials at the atomistic level are usually derived from assumptions based on experimental observations. In the present study, we employ computationally economical density functional theory (DFT)-based ab initio calculations for evaluating the physical properties of undoped and doped modifications of large-band-gap ceramics. Motivated by a recent experimental work, we have studied the thermodynamic and optoelectronic properties of pristine- and Ce4+-doped BaZrO3 compounds for selected concentrations of cerium dopant (x = 0, 0.037, and 0.125). Our results provide a clear insight into the relationship between dopant concentration x and the improved optical properties of BaZr1–xCexO3 compounds, which is directly related to the enhancement of their photocatalytic activity. The physical properties of Ce4+-doped BaZrO3 ceramics obtained using DFT calculations are not only found to be in good agreement with experiment, but can also provide a deeper understanding of their tunable optoelectronic properties, which can be tailored to attain functionalities required for practical applications. Based on our results, we conclude that modern DFT can serve as an efficient tool for predicting ceramic photocatalysts suitable for advancing hybrid advanced oxidation processes of sonochemistry.