Highly nitrogen-doped porous carbon transformed from graphitic carbon nitride for efficient metal-free catalysis

Abstract

Nitrogen-doped carbon materials are proposed as promising metal-free catalysts for persulfate-mediated catalytic oxidation process, yet the nitrogen content in the final carbon products is typically low. Moreover, controversies remain in the unambiguous identification of active sites in nitrogen-doped carbons for persulfate activation. Here we report the facile synthesis of nitrogen-doped carbon material via one-step pyrolysis of urea and D-mannitol, which simultaneously combine ultrahigh nitrogen content (up to 33.75 at%) with apparent porous structure via transformation from graphitic carbon nitride. With this strategy, the highly nitrogen-doped porous carbon (NC_1.0) exhibits excellent catalytic activity toward peroxymonosulfate (PMS) activation for oxidation of organic pollutants. Both experiments and density functional theory (DFT) calculations, for the first time, revealed that the electron-rich graphitic N and electron-deficient carbon atom adjacent to graphitic N in NC_1.0 served as active sites for PMS reduction and oxidation toward the generation of hydroxyl radical (OH) and singlet oxygen (¹O₂), respectively, in which PMS oxidation was the main reaction in the course of PMS activation rendering ¹O₂ the dominant reactive oxygen species (ROS) in the NC_1.0/PMS system. More importantly, NC_1.0 presents robust stability in PMS activation, superior to most reported nitrogen-doped carbon-based catalysts, offering great promise for practical environmental remediation.

Keywords: Electron transfer; Graphitic carbon nitride; Metal-free catalysis; N-doped porous carbon; Peroxymonosulfate.