Mechanism of the Desulfurization Route of the Reduction of SO2 on Carbons. Dimerization of Disulfur and Tetrasulfur

The desulfurization of carbons modified with SO2 was studied as a dispersion in boiling cyclohexane (81°C) using activated carbon (mAC) and graphene oxide (mGO), modified by SO2. The steady‐state species in the carbon matrix after the catalytic reduction of SO2 was considered a trisulfane. For mAC, there was a burst of a sulfur species identified as S2 by UV spectrum with a maximum at 217 nm (εM at 217 nm = 2.56 × 103) that showed a second‐order decay of absorbance with = 47.29 M‐1·sec‐1 (= 18.1 kcal·mol‐1). The product was postulated to be S4. No other consecutive reaction was observed because of the possible adsorption of S4 in the carbon matrix. The desulfurization of mGO was shown by XPS and the kinetics were a second‐order decay up to 16 min ( 18.41 M‐1·sec‐1;= 18.8 kcal·mol‐1) followed by a second‐order increase of absorbance with = 3.84 M‐1·sec‐1 (= 19.9), where the product showed a double maximum at 260‐285 nm typical of S8. These results are consistent with a mechanism of consecutive thermodynamically favorable dimerizations of S2 and S4 and with the desulfurization mechanism that has been previously postulated.