Critical Impact of Nitrogen Vacancies in Nonradical Carbocatalysis on Nitrogen-Doped Graphitic Biochar.

Nitrogen-doped graphitic biochar (NBC) has boosted the development of nonradical peroxymonosulfate (PMS) activation in environmental remediation. However, the specific role of nitrogen species played in NBC-based nonradical carbocatalysis remains vaguely interpreted. To pinpoint the critical nitrogen speciation, a sophisticated thermo-mechanochemical manipulation was exploited to prepare a series of NBCs with similar dimensional structures and oxygen levels but different nitrogen species (i.e., dopants and vacancies). Different from conventional perspectives, nonradical NBC-based carbocatalysis was found to be preferably determined by the nitrogen vacancies more than their parent nitrogen dopants. Raman depth analysis evidenced that a complete transformation of nitrogen dopants into nitrogen vacancies could be achieved at 800 °C, where an excellent nonradical abatement of 4-chlorophenol (4-CH, 90.9% removal) was found for the NBC800 with a low PMS consumption (1.24 mM). According to PMS adsorption experiments, nitrogen vacancies exhibited the highest affinity toward the PMS molecules compared to nitrogen dopants, which accounted for the superior carbocatalysis. Electron paramagnetic resonance and Raman spectroscopic analyses indicated that the original PMS molecules were bound to positively charged nitrogen vacancies, and a robust metastable complex (*HSO5-) evolved subsequently via hydrogen abstraction by adjacent persistent free radicals. In situ Raman techniques could be adopted to estimate the level of nitrogen vacancies associated with the polarization of electron distribution. The flexible feature and practical prospects of nitrogen vacancy-based carbocatalysis were also observed in the remediation of simulated phenolic industrial wastewater. Overall, this study unravels the dilemma in the current NBC-based nonradical carbocatalysis and advances our understanding of nitrogen doping technology for next-generation biochar design.