Ultrasmall mesoporous nanoparticles (< 50 nm), a unique porous nanomaterial, have been widely studied in the last decade owing to the abundant advantages, involving rich mesopores, low density, high surface area, numerous reaction sites, large cavity space, ultrasmall size, etc. It has been widely used in a range of applications, involving absorption, catalysis, energy storage, fluorescence imaging, and drug delivery/therapy. This paper presents a review of recent advances in the preparation, functionalization and applications of ultrasmall inorganic mesoporous nanoparticles for the first time. The soft monomicelles‐directed method, in contrast to the hard‐template and template‐free methods, is more flexible in the synthesis of mesoporous nanoparticles. This is because the amphiphilic micelle has tunable functional blocks, controlled molecule masses, and adjusted configurations and mesostructures. Focus on the soft micelle directing method, monomicelles could be classified into four types, i.e., the Pluronic‐type block copolymer monomicelles, laboratory‐synthesized amphiphilic block copolymers monomicelles, the single‐molecule star‐shaped block copolymer monomicelles, and the small‐molecule anionic/cationic surfactant monomicelles. This paper also reviews the functionalization of the inner mesopores and the outer surfaces, which includes constructing the yolk‐shell structures (encapsulated nanoparticles), anchoring the active components packed on the shell and building an asymmetric Janus architecture. Then, several representative applications, involving catalysis, energy storage, and biomedicines are presented. Finally, the prospects and challenges of controlled synthesis and large‐scale applications of ultrasmall mesoporous nanoparticles in the future are foreseen.
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