Superstructured Macroporous Carbon Rods Composed of Defective Graphitic Nanosheets for Efficient Oxygen Reduction Reaction

Rationally designed carbon materials with superstructures are promising candidates in applications such as electrocatalysis. However, the synthesis of highly porous carbon superstructures with macropores and carbon defects from a simple crystalline solid remains challenging. In this work, superstructured macroporous carbon rods composed of defective graphitic nanosheets are synthesized by direct carbonization of crystalline poly tannic acid (PTA) rods as precursors. During carbonization, PTA rods with a highly ordered lamellar structure induce a spatially confined two‐step localized contraction that takes place in different dimensions and directions in each step. The unexpected contraction behavior results in the sponge‐like macroporous carbon superstructure with large surface area, high porosity, and abundant defects, thus showing a superior electrocatalytic performance with high activity and selectivity for oxygen reduction reaction. The study provides new understandings in the design of functional carbon materials with distinctive structures and applications. Superstructured macroporous carbon rods composed of defective graphitic nanosheets are synthesized by direct carbonization of crystalline poly tannic acid rods as a new carbon precursor. A spatially confined two‐step localized contraction mechanism is proposed for the simultaneous formation of macroporous superstructure and defects, resulting in a remarkable oxygen reduction reaction performance.