Diesel soot photooxidation enhances the heterogeneous formation of H₂SO₄

Both field observation and experimental simulation have implied that black carbon or soot plays a remarkable role in the catalytic oxidation of SO₂ for the formation of atmospheric sulfate. However, the catalytic mechanism remains ambiguous, especially that under light irradiation. Here we systematically investigate the heterogeneous conversion of SO₂ on diesel soot or black carbon (DBC) under light irradiation. The experimental results show that the presence of DBC under light irradiation can significantly promote the heterogeneous conversion of SO₂ to H₂SO₄, mainly through the heterogeneous reaction between SO₂ and photo-induced OH radicals. The detected photo-chemical behaviors on DBC suggest that OH radical formation is closely related to the abstraction and transfer of electrons in DBC and the formation of reactive superoxide radical (•O₂^-) as an intermediate. Our results extend the known sources of atmospheric H₂SO₄ and provide insight into the internal photochemical oxidation mechanism of SO₂ on DBC.