Insight to the mechanism of tetracycline removal by ball-milled nanocomposite CeO2/Fe3O4/Biochar: Overlooked degradation behavior
A novel nanocomposite CeO 2 /Fe 3 O 4 /biochar (BC) was prepared using a straightforward, solvent-free mechanical ball milling method. Comparatively to the material prepared by chemical co-precipitation (77.14 %) and raw BC (33.64 %), CeO 2 /Fe 3 O 4 /BC prepared by ball milling achieved better tetracycline (TC) removal (94.35 %) under the optimal condition (TC concentration 10 mg·L -1 , catalyst dose 0.5 g·L -1 and pH 9.01). Ball milling not only reduced the particle size, but also increased the surface area of composite, which was favorable to the adsorption of TC on CeO 2 /Fe 3 O 4 /BC. Meanwhile, the number of oxygen-containing functional groups in as-prepared nanocomposite increased after ball milling, which could serve as the bridge of electron transfer to enhance TC degradation. Dissolved oxygen (DO) was activated by CeO 2 /Fe 3 O 4 /BC to produce reactive oxygen species (ROS) for the TC degradation. X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) characterization indicated that the enhanced oxygen activation should be attributed to the presence of Ce 4+ /Ce 3+ and Fe 3+ /Fe 2+ redox pairs and persistent free radicals (PFRs) in CeO 2 /Fe 3 O 4 /BC. Desorption experiments suggested that the adsorption and degradation induced by ball-milled CeO 2 /Fe 3 O 4 /BC were accounted for about 79.8 % and 20.2 % of total TC removal, respectively. This study revealed that the organic pollutants removal by BC-based nanocomposite is not alone contribution of the adsorption and the degradation behavior during this process should be concerned.
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