Heteroatom-doped carbon materials have demonstrated unique chemical properties compared to their parent carbon counterparts making them a promising alternative to traditional materials for a wide range of catalytic applications. However, precisely controlling the structure of heteroatom dopants remains a major challenge, as the current synthetic approaches typically yield a mixture of diverse configurations. This complexity has limited both our fundamental understanding of their roles and our ability to fully harness the potential of heteroatom-doped carbon materials as catalysts. Using a novel model platform, we investigated the thermodynamic behavior of different nitrogen configurations which are pyridinic, pyrrolic, and graphitic N. We found that, regardless of the starting state, the system eventually converges to a thermodynamically favorable state characterized by a mixture of pyridinic, pyrrolic, and graphitic N. Achieving complete specificity in nitrogen configuration requires kinetically stabilizing the N states derived from the precursor. By decoupling heteroatom incorporation from carbonization, we achieved precise control over nitrogen configurations across a wide range of carbon materials with varied structures and morphologies. Using N-doped carbons with 100% specificity in nitrogen configuration, we revealed the intrinsic activity of individual N-dopants for CO2 electroreduction to CO.
