The synthesized and thermally modified Mn–Ca–FeOOH composite in persulfate system: Its role to discolor methylene blue

Abstract

Methylene blue (MB) discoloration was performed using persulfate (PS) activated with the synthesized composites. Four types of composites, which were synthesized by the immobilization of Mn on iron oxides (hematite and goethite) using either NaOH or Ca(OH)2, were evaluated as PS activator. The synthesized Mn–Ca–FeOOH composite was selected and it was thermally modified at 300 and 700°C (denoted Mn–Ca–FeOOH_300 and Mn–Ca–FeOOH_700). The BET surface area of Mn–Ca–FeOOH_300 was similar to that of Mn–Ca–FeOOH while that of Mn–Ca–FeOOH_700 was dramatically lower. XRD and XPS analysis indicated that the thermal modification transformed iron oxides from goethite to hematite and changed amorphous manganese oxide to crystalline. MB discoloration at pH 3 indicated that Mn–Ca–FeOOH acted as an oxidant to degrade MB, and the thermally modified composites (i.e. Mn–Ca–FeOOH_300 and Mn–Ca–FeOOH_700) acted as a catalyst to activate PS. Moreover, incomplete MB discoloration was observed in PS/composite system at pH 3. However, a whole tested wavelength of MB was reduced when MB discoloration was tested in PS/composite system above pH 7. Moreover, the increasing pH of solution increased MB discoloration. The higher MB discoloration in heterogeneous system at pH 12 could suggest that superoxide anion (O2•−) was dominant reactive oxygen species.