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Developing economical and active materials is of great significance for VOC purification. Here, hierarchical porous Al 2 O 3 and ZnO microspheres (Al 2 O 3 -pm and ZnO-pm) were synthesized by a facile hydrothermal strategy. The urchin-like Al 2 O 3 -pm and flower-like ZnO-pm possess high specific surface area (especially; external surface area) obviously boost the dispersion of Pd with 29.3 % and 30.1 % over Pd/Al 2 O 3 -pm and Pd/ZnO-pm, respectively, over 3.4 times higher than those of commercial Al 2 O 3 - and ZnO-supported counterparts. Pd/Al 2 O 3 -pm possesses excellent activity and CO 2 yield in ethyl acetate (EA) degradation, with TOF reaches 7.76 × 10 -3 s -1 at 160 °C under GHSV of 50,000 h -1 . Moreover, Pd/Al 2 O 3 -pm exhibits satisfied performance in EA-contained binary VOCs oxidation and has high long-term stability under both dry and humid conditions. Both Pd sites and Brønsted acid sites participated in reaction process and initially react with EA to form ethylene and ethanol, respectively. Larger amount Brønsted acid sites over Pd/Al 2 O 3 -pm promote ethanol formation and C-C cleavage, resulting in different CO 2 yields and EA activation mechanisms. The coating greatly enhances Pd dispersion over Pd supported monolithic catalyst, endowing its desired activity and stability even with a much lower Pd loading. This work promotes the potential application of noble-metal-based monolithic materials in VOC degradation., (Copyright © 2020 Elsevier B.V. All rights reserved.)