Peroxymonosulfate activation by algal carbocatalyst for organic dye oxidation: Insights into experimental and theoretical

Preparation of nitrogen-doped algal carbocatalyst (NC) for peroxymonosulfate (PMS) activation to oxidative degrade methylene blue (MB), and the mechanism of radical and nonradical pathway in N-C/PMS system are investigated. Firstly, a series of N-doped carbonaceous materials (NC) were prepared using nitrogen-rich Taihu blue algae biomass as precursor at different annealing temperatures. It was found that the NC prepared by annealing at 800 °C (N-C-8) showed an optimal MB degradation performance of over 99% after 60 min. Confirmed by electron paramagnetic resonance (EPR) analyses and radical quenching experiments, radical and nonradical pathway (1O2 oxidation and electron-transfer) are both involved in MB degraded process. Moreover, both graphitic N derived from the intrinsic Taihu blue algae, and nitrogen vacancy evolved from nitrogen dopants decomposition exhibited high correlation with the MB removal rate in the N-C/PMS system. Finally, three possible degradation pathways of MB were proposed based on the Density Functional Theory (DFT) calculation and identified intermediates. Overall, this work provides a new insight into the intrinsic roles of nitrogen-dopants and nitrogen vacancies on the as-prepared carbocatalyst for PMS activation, and advances the understanding of the resource utilization of algal biomass.