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Mesoporous silica shells were formed on nonporous spherical silica cores during the sol-gel reaction to elucidate the mechanism for the generation of secondary particles that disturb the efficient growth of mesoporous shells on the cores. Sodium bromide (NaBr) was used as a typical electrolyte for the sol-gel reaction to increase the ionic strength of the reactant solution, which effectively suppressed the generation of secondary particles during the reaction wherein a uniform mesoporous shell was formed on the spherical core. The number