N-doped hierarchically porous carbon for highly efficient metal-free catalytic activation of peroxymonosulfate in water: A non-radical mechanism.

Metal-free carbo-catalyst has recently emerged as a promising candidate as a substituent for tradition-metal based heterogeneous catalyst for catalytic activation of peroxymonosulfate (PMS). However, most reported carbo-catalysts suffer from low catalytic efficiency and poor stability, thus a high-performance catalyst is urgently desired. In this study, a novel carbo-catalyst (NHPC-800), prepared by using tannic acid and dicyandiamide as renewable carbon/nitrogen feedstocks via a simple pyrolysis route, is reported as an activator of PMS with highly efficient catalytic ability and stability. The as-prepared NHPC-800 possesses as high as 22.4 atom% of nitrogen dopants and a hierarchically porous structure with abundant meso/macropores, accompanied by the abundant edges and wrinkles, which supply sufficient exposed catalytically active centers and fast electrons/mass transportations. Using rhodamine B as a model pollutant, the NHPC-800 shows a highly efficient catalytic ability which is superior to most reported carbo-catalysts and even some state-of-the-art metal catalysts. Based on competitive quenching experiments and electron paramagnetic resonance (EPR) results, a non-radical pathway involving the generation of 1O2 is responsible for the degradation of pollutants. Given that the NHPC-800 shows good recycling performance and strong resistance to adventitious interference such as anions and natural organic matters, we believe NHPC-800 can be a promising candidate for practical applications, and this study can provide inspirations for the further development of highly efficient carbo-catalysts.

Oxidation of organic contaminant in a self-driven electro/natural maghemite/peroxydisulfate system: Efficiency and mechanism.

Electro-assisted iron-mediated persulfate (PS) activation process has been successfully employed to oxidize organic contaminant. However, a majority of iron-based catalysts used for PS activation was synthesized through complicated or demanding procedures and may have potential risks on environment during the preparation process. Herein, natural maghemite (NM) which is abundant on the earth was employed to activate peroxydisulfate (PDS) in an electrolytic cell. The voltage was provided by microbial fuel cell (MFC) instead of external power as reported in the previous studies, so as to establish a self-driven electro/natural maghemite/PDS system (MFC/NM/PDS) for the oxidation of acid orange 7 (AO7). The results showed that above 90% removal efficiency of AO7 was achieved in a wide range of pH (3.0-9.0) after 100min reaction. Singlet oxygen was identified for the first time during PDS activation and surface bound sulfate radicals served as the dominant active species responsible for AO7 oxidation. The underlying mechanism of AO7 elimination in the MFC/NM/PDS system was elucidated through quenching tests, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) techniques. The variation of TOC and cytotoxicity to Escherichia coli was explored. The intermediate products formed were identified using LC-TOF-MS technique and a possible pathway of AO7 degradation was proposed.