Hollow MnO2 architectures exhibit enhanced catalytic performance for volatile organic compound removal

• Hollow MnO 2 microcuboids outperform 1% Pt/Al 2 O 3 in benzene oxidation catalysis. • Oxygen vacancies in hollow MnO 2 boost benzene oxidation efficiency. • Hollow structure’s capillary action concentrates reactants, enhancing catalysis. • Hollow MnO 2 ′s remarkable stability makes it promising for real-world use. Tackling the urgent need for efficient catalytic abatement of harmful volatile organic compounds (VOCs), this study presents the controlled synthesis of hollow MnO 2 microcuboids with hierarchical structures for enhanced benzene oxidation catalysis . The hollow MnO 2 catalysts, obtained via a redox reaction between MnCO 3 precursors and KMnO 4 followed by selective acid etching, exhibit significantly higher surface area, oxygen defects, and Mn 3+ concentration compared to solid MnO 2 . Comprehensive characterization techniques reveal the structure–activity relationships governing the superior catalytic performance, which rivals that of a 1 % Pt/Al 2 O 3 reference catalyst. The unique hollow morphology, comprising thin shell walls built from interconnected nanorods, substantially enhances active site accessibility and lowers the activation energy barrier. A key feature of the hollow structure is its ability to concentrate reactants within the confined internal void through capillary action, a phenomenon that enriches reactant concentrations and further promotes catalytic activity. In-situ DRIFTS analyses provide mechanistic insights into surface species transformations during benzene oxidation. Notably, the hollow MnO 2 catalyst demonstrates impressive long-term stability and high activity in the presence of water vapor, highlighting its potential for practical industrial VOC abatement applications.