Insights into the Mechanism of Ozone Activation and Singlet Oxygen Generation on N-Doped Defective Nanocarbons: A DFT and Machine Learning Study

N-doped defective nanocarbon (N-DNC) catalysts have been widely studied due to their exceptional catalytic activity in many applications, but the O₃ activation mechanism in catalytic ozonation of N-DNCs has yet to be established. In this study, we systematically mapped out the detailed reaction pathways of O₃ activation on 10 potential active sites of 8 representative configurations of N-DNCs, including the pyridinic N, pyrrolic N, N on edge, and porphyrinic N, based on the results of density functional theory (DFT) calculations. The DFT results indicate that O₃ decomposes into an adsorbed atomic oxygen species (O_ads) and an ³O₂ on the active sites. The atomic charge and spin population on the O_ads species indicate that it may not only act as an initiator for generating reactive oxygen species (ROS) but also directly attack the organics on the pyrrolic N. On the N site and C site of the N₄V₂ system (quadri-pyridinic N with two vacancies) and the pyridinic N site at edge, O₃ could be activated into ¹O₂ in addition to ³O₂. The N₄V₂ system was predicted to have the best activity among the N-DNCs studied. Based on the DFT results, machine learning models were utilized to correlate the O₃ activation activity with the local and global properties of the catalyst surfaces. Among the models, XGBoost performed the best, with the condensed dual descriptor being the most important feature.