Morphology-dependent activation of hydrogen peroxide with Cu2O for tetracycline hydrochloride degradation in bicarbonate aqueous solution

The design of efficient heterogeneous catalysts in bicarbonate-activated hydrogen peroxide systems (BAP) is a hot topic in wastewater treatment. In this work, Cu2O nanoparticles with different morphologies including cubic shape (c-Cu2O), octahedron shape (o-Cu2O) and spherical shape (s-Cu2O), were applied in BAP for the first time to degrade tetracycline hydrochloride (TC). Compared with Cu2+ ions and CuO, TC degradation was boosted in the presence of Cu2O in the BAP system, with the degradation rate following the order c-Cu2O > o-Cu2O > s-Cu2O. The morphology-dependent effects could be linearly correlated with the ratio of surface oxygen species (OS), but not with the surface area or Cu(I) ratio. The c-Cu2O catalyst with exposure of (100) facets contained 76.6% OS as the active site for H2O2 adsorption and activation, while the value was much lower for o-Cu2O and s-Cu2O with dominant (111) facets. The presence of HCO3− enhanced the interactions among Cu2O, H2O2 and TC, leading to facile oxidation of Cu(I) to Cu(II) by H2O2, and the formation of various reactive species such as hydroxyl radicals and Cu(III) contributed to TC degradation. This work provides a new method for enhancing H2O2 activation with heterogeneous catalysts by crystal facet engineering.