Self‐Limiting Synthesis of Supported Nanoparticle Superlattices on Diverse Substrates via Surface Coordination Chemistry

Abstract High‐loading, uniformly dispersed nanoparticles (NPs) on functional substrates are vital for advanced catalysis and energy storage, yet remain difficult to realize because of particle aggregation, size polydispersity, and weak interfacial binding. Herein, a versatile and scalable self‐limiting synthesis strategy based on surface coordination chemistry is presented to fabricate compositionally tunable NP superlattices on a broad range of substrates—including carbon nanotubes, graphene oxide, carbon fibers, silicon wafers, and natural shells. This approach leverages the selective adsorption of sodium oleate onto substrate surfaces through hydrogen bonding between its carboxyl groups and surface hydroxyl or carboxyl groups, creating a reactive interface for site‐specific cation exchange with mono‐ to multinary metal ions. Subsequent pyrolysis converts the exchanged layer into NPs, while the self‐limiting mechanism—driven by precursor exhaustion and ligand passivation—ensures uniform NP sizes and spontaneous assembly into ordered superlattices. As a functional demonstration, high‐density deposition of complex FeMnCoZnCeNiO x NPs on commercial carbon nanotubes is achieved, showcasing their enhanced performance as catalytic sulfur hosts in lithium–sulfur batteries. This strategy offers a robust pathway to integrate precision nanochemistry with scalable materials processing, opening new possibilities for advanced energy storage and catalysis.