This paper reviews the progress made recently in synthesis and applications of spherical silica micro/nanomaterials with multilevel (hierarchical) structures. The spherical silica micro/nanomaterials with hierarchical structures are classified into four main structural categories that include (1) hollow mesoporous spheres, (2) core-in-(hollow porous shell) spheres, (3) hollow spheres with multiple porous shells and (4) hierarchically porous spheres. Due to the complex structures and being focused on spherical silica micro/nanomaterials, some novel methods based on the combination of two routine methods or two surfactants, and some special synthetic strategies are proposed to produce the spherical silica micro/nanomaterials with hierarchical structures. Compared with the same-sized solid, porous or hollow silica spheres, these fantastic spherical silica micro/nanomaterials with hierarchical structures exhibit enhanced properties which may enable them to be used in broad and promising applications as ideal scaffolds (carriers) for biological, medical, and catalytic applications.
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