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 (H 2 O 2 ) 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 H 2 O 2 (up to 96%), high mass activity of 545.5 A g −1 at 0.2 V versus RHE and stable production of H 2 O 2 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 H 2 O 2 . 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 H 2 O 2 through 2e − ORR rather than H 2 O via 4e − ORR. This work provides new insights for developing metal‐free catalysts for efficient electrosynthesis of H 2 O 2 using seawater resources as promising electrolytes.