Self-sacrificial biomass-derived silica is a rising and promising approach to fabricate large metal silicates, which are practical water treatment agents ascribed for easy sedimentation and separation. However, the original biomass architecture is difficult to be maintained and utilized. Furthermore, sufficient ion diffusion pathways need to be created to satisfy massive mass transport in large bulk materials. Herein, a series of metal silicates, including cobalt silicate (CoSiOx), copper silicate, nickel silicate, iron silicate, and magnesium silicate, are synthesized from Indocalamus tessellatus leaf as the biomass-derived silica source and investigated as catalysts in sulfate-radical-based advanced oxidization processes (SR-AOPs) for the first time. Among them, CoSiOx presents an analogical sandwich structure as a leaf-derived template of micron-level size. More importantly, the interior hollow nanotubes assembled by small nanosheets provide numerous pathways for ion diffusion and remarkably promote the mass transport in such large bulk materials. Owing to the combination of the unique structure with the high reactivity of Co (II) toward peroxymonosulfate, CoSiOx exhibits excellent catalytic performance with 0.242 and 0.153 min(-1) rate constants for the removal of methylene blue and phenol, respectively, which outperforms/is comparable to that of the reported nanomaterials toward organic contaminants in SR-AOPs. (C) 2019 Elsevier Inc. All rights reserved.