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Porous silicon has found wide applications in many different fields including catalysis and lithium-ion batteries. Three-dimensional hierarchical macro-/mesoporous silicon is synthesized from zero-dimensional Stöber silica particles through a facile and scalable magnesiothermic reduction process. By systematic structure characterization of the macro-/mesoporous silicon, a self-templating mechanism governing the formation of the porous silicon is proposed. Applications as lithium-ion battery anode and photocatalytic hydrogen evolution catalyst are demonstrated. It is found that the macro-/mesoporous silicon shows significantly improved cyclic and rate performance over the commercial nanosized and micrometer-sized silicon particles. After 300 cycles at 0.2 A g -1 , the reversible specific capacity is still retained as much as 959 mAh g -1 with a high mass loading density of 1.4 mg cm -2 . With the large current density of 2 A g -1 , a reversible capacity of 632 mAh g -1 is exhibited. The coexistence of both macro- and mesoporous structures is responsible for the enhanced performance. The macro-/mesoporous silicon also shows superior catalytic performance for photocatalytic hydrogen evolution compared to the silicon nanoparticles.

Self-Templating Construction of 3D Hierarchical Macro-/Mesoporous Silicon from 0D Silica Nanoparticles