The significant role of boron source for nitrogen doped carbon structure is demonstrated. Among variable synthesized structures, depending on their compositions of precursors via chlorination, hollow granular carbon structure is developed without any additional templates. It shows high CO2 capture properties with excellent selectivity.

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The introduction of heteroatoms into carbon materials has been widely used to boost the surface reactivity of carbon materials, and doping of boron and/or nitrogen is one of the most powerful strategies to modify the characteristics of carbon materials. Unlike nitrogen doping that has been extensively investigated, the influence of boron doping on the synthesis of porous carbon materials has not been comprehensively understood. In this study, we successfully synthesize heteroatom (boron, nitrogen, and/or oxygen)-doped highly nanoporous carbon materials via the chlorination process of a carbonitride–boride mixture without additional treatment. Boron atoms are readily diffused from boride to adjacent carbonitride-derived carbon during the chlorination process and function as atomic welders, which are the key to construct a heteroatom-rich nanoporous carbon structure. Oxygen-rich nanoporous carbon and nitrogen-rich nanoporous carbon can be selectively synthesized by controlling the raw carbonitride precursor composition. They show superior catalytic performance in the 2e– and 4e– pathway oxygen reduction reaction, respectively.

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