Mineral‐Precursor Morphology Modulates Si–O–C Catalytic Sites for Efficient Electron‐Transfer Water Treatment at Low Oxidant Dosage

ABSTRACT Precise electronic modulation of metal‐free catalysts is crucial for enhancing nonradical electron transfer processes (ETP) and enabling green Fenton‐like systems with minimized oxidant consumption. Herein, we demonstrate that the morphology of mineral precursors dictates the electronic configuration of Si–O–C catalytic sites. A series of carbon catalysts with distinct geometries but comparable active‐site densities were engineered using spherical silica, montmorillonite, zeolite, and kaolin as structural templates. Although all catalysts efficiently degraded tetracycline via peroxymonosulfate (PMS) activation at an ultralow dose (0.1 m m ), their ETP kinetics differed significantly. Electrochemical analysis and DFT calculations reveal that the inherited morphology directly regulates the lowest unoccupied molecular orbital (LUMO) energy of Si–O–C moieties. The spherical structure provides the most favorable LUMO position, minimizing the interfacial electron‐transfer barrier and leading to superior activity. This morphology–activity correlation enabled the design of a scalable, ETP‐dominated water treatment system, validated with tap, reclaimed, and lake water in a 20 L semi‐continuous reactor. This work offers a morphology‐guided electronic engineering strategy for efficient and sustainable water purification.