摘要： Hollow nanostructures are attractive for energy storage and conversion, drug delivery, and catalysis applications. Although these hollow nanostructures of compounds can be generated through the processes involving the well-established Kirkendall effect or ion exchange method, a similar process for the synthesis of the pure-substance one (e.g., Si) remains elusive. Inspired by the above two methods, we introduce a continuous ultrathin carbon layer on the silica nano/microstructures (St?ber spheres, diatom frustules, sphere in sphere) as the stable reaction interface. With the layer as the diffusion mediator of the reactants, silica structures are successfully reduced into their porous silicon hollow counterparts with metal Al powder in AlCl3?NaCl molten salt. The structures are composed of silicon nanocrystallites with sizes of 15?25 nm. The formation mechanism can be explained as an etching?reduction/nucleation?growth process. When used as the anode material, the silicon hollow structure from diatom frustules delivers specific capacities of 2179, 1988, 1798, 1505, 1240, and 974 mA h g?1 at 0.5, 1, 2, 4, 6, and 8 A g?1, respectively. After being prelithiated, it retains 80% of the initial capacity after 1100 cycles at 8 A g?1. This work provides a general way to synthesize versatile silicon hollow structures for high-performance lithium ion batteries due to the existence of ample silica reactants and can be extended to the synthesis of hollow structures of other materials.