Tuning Mechanistic Pathways and Ion Selectivity in Micellar Catalysis—A Review

Micellar catalysis has evolved from a classical colloidal phenomenon into a sophisticated supramolecular strategy for manipulating chemical reactivity through nanoscale interfacial engineering. While early models attributed catalytic acceleration primarily to reactant concentration within confined pseudophases, contemporary investigations reveal that reactivity is governed by a complex interplay of counterion binding, interfacial hydration, and dynamic morphological transitions. This review provides a critical appraisal of the mechanistic foundations of ion selectivity in micellar catalysis, with particular emphasis on cationic surfactant systems and the seminal semi‐empirical kinetic frameworks. By synthesizing advanced experimental evidence from cryo‐TEM, rheo‐SAXS, and kinetic modeling, we elucidate how hydrophobic and aromatic counterions dictate micellar restructuring and catalytic pathway modulation via hydrophobic insertion and π‐cation interactions. Furthermore, we address current bottlenecks in scalability, reproducibility, and toxicity, while highlighting emerging frontiers such as machine learning‐guided surfactant design, stimuli‐responsive assemblies, and green nanoreactors. Ultimately, this review establishes ion selectivity as a foundational principle for modern colloid chemistry, offering a comprehensive blueprint for the design of precision‐controlled, sustainable supramolecular catalysts.