Size‐Dependent Catalysis in Fenton‐like Chemistry: From Nanoparticles to Single Atoms

Abstract State‐of‐the‐art Fenton‐like reactions are crucial in advanced oxidation processes (AOPs) for water purification. This review explores the latest advancements in heterogeneous metal‐based catalysts within AOPs, covering nanoparticles (NPs), single‐atom catalysts (SACs), and ultra‐small atom clusters. A distinct connection between the physical properties of these catalysts, such as size, degree of unsaturation, electronic structure, and oxidation state, and their impacts on catalytic behavior and efficacy in Fenton‐like reactions. In‐depth comparative analysis of metal NPs and SACs is conducted focusing on how particle size variations and metal‐support interactions affect oxidation species and pathways. The review highlights the cutting‐edge characterization techniques and theoretical calculations, indispensable for deciphering the complex electronic and structural characteristics of active sites in downsized metal particles. Additionally, the review underscores innovative strategies for immobilizing these catalysts onto membrane surfaces, offering a solution to the inherent challenges of powdered catalysts. Recent advances in pilot‐scale or engineering applications of Fenton‐like‐based devices are also summarized for the first time. The paper concludes by charting new research directions, emphasizing advanced catalyst design, precise identification of reactive oxygen species, and in‐depth mechanistic studies. These efforts aim to enhance the application potential of nanotechnology‐based AOPs in real‐world wastewater treatment.