High-entropy carbons: From high-entropy aromatic species to single-atom catalysts for electrocatalysis

Single-atom catalysts (SACs) have rapidly entered the field of nanomaterials and demonstrated great potential for energy devices in recent years. Of all types of SACs, porous carbon-based SACs are the most popular species because of their excellent conductivity, large specific surface area, and easily tunable heteroatom and metal components. However, most of the reported cases focus on the metal centers and their coordination environments, while they do not pay much attention to carbon precursors and carbon transformation during hightemperature treatment. In this work, we use a high-entropy aromatic molecule, azulene, for rational synthesis of azulene-enriched, sandwich-like polymer nanosheets and corresponding single-Fe-dispersed porous carbon nanosheets. The azulene-based metal-free polymer nanosheets exhibit a narrow band gap and temperaturedependent magnetism. As proof-of-concept electrocatalysts for CO2 reduction, the prepared carbon nanosheets exhibit high activity and stability. Operando X-ray absorption spectroscopy and density functional theory studies reveal the high activity of Fe-N coordination sites in the presence of 5/7-membered carbon ring-based topological defects in the carbon skeleton. Taken together, this work provides a new method of synthesizing highentropy carbons using azulene-based high-entropy molecule as precursor and paves the way toward highefficiency SACs with rich topological defects for energy conversion.

Automated summary

This study synthesized azulene-enriched polymer nanosheets and single-iron dispersed porous carbon nanosheets using azulene as a precursor, which showed high activity and stability as electrocatalysts for CO2 reduction. The presence of topological defects with 5/7-membered carbon rings in the carbon skeleton was found to enhance the activity of Fe-N coordination sites, paving the way for efficient single-atom catalysts with rich topological defects for energy conversion.