Multi‐Scale Engineered 2D Carbon Polyhedron Array with Enhanced Electrocatalytic Performance

Abstract Electrocatalyst engineering from the atomic to macroscopic level of electrocatalysts is one of the most powerful routes to boost the performance of electrochemical devices. However, multi‐scale structure engineering mainly focuses on the range of atomic‐to‐particle scale such as hierarchical porosity engineering, while catalyst engineering at the macroscopic level, such as the arrangement configuration of nanoparticles, is often overlooked. Here, a 2D carbon polyhedron array with a multi‐scale engineered structure via facile chemical etching, ice‐templating induced self‐assembly, and high‐temperature pyrolysis processes is reported. Controlled phytic acid etching of the carbon precursor introduces homogeneous atomic phosphorous and nitrogen doping, as well as a well‐defined mesoporous structure. Subsequent ice‐templated self‐assembly triggers the formation of a 2D particle array superstructure. The atomic‐level doping gives rise to high intrinsic activity, while the well‐engineered porous structure and particle arrangement addresses the mass transport limitations at the microscopic particle level and macroscopic electrode level. As a result, the as‐prepared electrocatalyst delivers outstanding performance toward oxygen reduction reaction in both acidic and alkaline media, which is better than recently reported state‐of‐the‐art metal‐free electrocatalysts. Molecular dynamics simulation together with extensive characterizations indicate that the performance enhancement originates from multi‐scale structural synergy.