Hydrogenated Pyridine‐Pyrrole Nitrogen‐Doped Carbon for High‐Efficiency Electrosynthesis of Hydrogen Peroxide in NaCl Electrolyte

Abstract Developing metal‐free carbon catalysts is critical to achieve the electrosynthesis of hydrogen peroxide (H₂O₂) via two‐electron oxygen reduction reaction (2e⁻ ORR) using seawater as electrolyte. Herein, N‐rich doped carbon (NC) is synthesized by directly pyrolyzing guanine as both N and C sources, which can facilitate the formation of ultrahigh‐N dopant (up to 33.89 at.%), and their ratios. The NC obtained at 700 °C with hydrogenated pyridine‐N and pyrrole‐N (3:2) dopants exhibits a superior selectivity of H₂O₂ (up to 96%), high mass activity of 545.5 A g⁻¹ at 0.2 V versus RHE and stable production of H₂O₂ with 16.8 in 0.5 M NaCl. In situ Fourier transform infrared spectrum analysis proves that hydrogenated pyridine‐N and pyrrole‐N dopants play a critical role in constructing metal‐free active sites for the synthesis of H₂O₂. Meanwhile, theoretical calculations further reveal that compared to non‐hydrogenated N dopants, hydrogenated pyridine and pyrrole N can tune the projected density of states of 2p_z orbitals of their adjacent carbon atoms approaching Fermi Level, enhancing ^*OOH to H₂O₂ through 2e⁻ ORR rather than H₂O via 4e⁻ ORR. This work provides new insights for developing metal‐free catalysts for efficient electrosynthesis of H₂O₂ using seawater resources as promising electrolytes.