Radicals in the Mechanochemical Dechlorination of Hazardous Organochlorine Compounds Using CaO Nanoparticles

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Abstract
For the first time, we detected paramagnetic products generated during the grinding of 3-chlorobiphenyl (BP-Cl) with calcium oxide (CaO) nanoparticles by a ball mill method, which is one of the promising ways to detoxify hazardous chlorinated organic compounds. Those products were assigned to oxygen-centered aromatic radicals coming from BP-Cl and trapped electrons in oxygen vacancies on the surfaces of the CaO reactants using high-frequency and pulsed electron paramagnetic resonance spectroscopies. The observed good correlation between the dechlorination efficiency and the radical yield suggests that a radical mechanism plays an important role in the destruction of organochlorine compounds. The mechanochemical dechlorination could be interpreted by the following mechanism. First of all, the mechanical stressing induces the electron transfer from O2− sites on the surface of the CaO particle to the organic compounds. The produced organic anion radicals then undergo the effective self-dissociation of a chlorine–carbon bond.

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