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

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 molgcat−1h−1${\rm{mol}}\;{\rm{g}}_{{\rm{cat}}}^{ - 1}{{{\rm{h}}}^{ - 1}}$ 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 2pz 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. Hydrogenated pyridine‐pyrrole N doped carbon synthesized by directly pyrolyzing guanine demonstrates dual active sites of hydrogenated‐N induce adjacent carbon atoms for electrosynthesis of H2O2 in NaCl electrolyte, exhibiting high selectivity of ≈96% and H2O2 production yield of 16.8 molgcat−1h−1${\rm{mol}}\;{\rm{g}}_{{\rm{cat}}}^{ - 1}{{{\rm{h}}}^{ - 1}}$.