Enhancing plasma-catalytic toluene oxidation: Unraveling the role of Lewis-acid sites on δ-MnO2

The emission of volatile organic compounds (VOCs) into the air, primarily due to human activities, has caused significant environmental pollution and health concerns. In response, the development of advanced environmental catalysts is crucial, and δ-MnO2 has emerged as a promising material for efficient VOC oxidation. However, the identification of the specific active sites and the underlying oxidation mechanisms of this material remain unclear, hindering the development and optimization of high-activity catalysts. Herein, we present a strategy to remove the internal water and hydrated cations from δ-MnO2, thereby unblocking the inter-lamellar gaps and exposing the internal Lewis-acid sites, while maintaining other physical and chemical characteristics of the sample unchanged. Notably, the well-defined δ-MnO2 catalysts with more accessible interlayer Lewis-acid sites exhibited significantly enhanced catalytic activity in toluene oxidation, demonstrated in both two-stage plasma catalysis and single-stage ozonation processes. A quantitative analysis of Lewis-acid sites and initial toluene reaction rates revealed that these Lewis-acid sites serve as the active centers for toluene adsorption and activation, and the heterogeneous reaction between toluene and ozone follows the Langmuir-Hinshelwood mechanism. Moreover, in-depth analysis of byproducts showed that δ-MnO2 rich in Lewis-acid sites promoted the oxidation of intermediates, such as esters, hydrazides, and ketones, leading to a more complete toluene oxidation. This work not only fully explores the potential of δ-MnO2 as a catalyst, but also provides valuable insights into the elucidation of unknown catalytic active sites, potentially paving the way for the rational design of more efficient catalysts for VOC oxidation.