Evolution of Surface Catalytic Sites on Bimetal Silica-Based Fenton-Like Catalysts for Degradation of Dyes with Different Molecular Charges.

We present here important new findings on the direct synthesis of bimetal Cu-Mn containing porous silica catalyst and the effects of structure-directing agent removal from the prepared nanomaterial on the evolution of surface catalytic sites. The extraction-calcination procedure of the structure-directing agent removal led to the formation of Cu and Mn oxo-clusters and Cu and Mn oxide nanoparticles smaller than 5 nm, while the solely calcination procedure led to the mentioned species and in addition to the appearance of CuO nanoparticles 20 nm in size. Catalysts were tested in the Fenton-like catalytic degradation of dyes with different molecular charge (cationic, anionic, and zwitterionic) as model organic pollutants in wastewater at neutral pH. Significantly faster degradation of cationic and anionic dyes in the first 60 min was observed with the catalyst containing larger CuO nanoparticles (>20 nm) due to the less hindered generation of OH radicals and slower obstructing of the active sites on the catalysts surface by intermediates. However, this was not found beneficial for zwitterionic dye with no adsorption on the catalysts surface, where the catalyst with smaller Cu species performed better.