A comparative study on high-efficient reduction of bromate in neutral solution using zero-valent Al treated by different procedures

Bromate, a toxic by-product of bromide-containing drinking water after disinfecting with ozone, has attracted much attention in the past two decades. Traditional methods to activate zero-valent metals for reducing bromate are to eliminate their surface oxide layer by acid washing. In this work, for the first time, zero-valent Al (ZVAl) was surface treated by the following procedures including soaking, soaking and freeze-drying, soaking and heat-treating, and γ-Al2O3 covering Al particle surfaces (GCAP). It was found that all of above surface treated ZVAls have an obvious high efficiency for bromate reduction relative to pristine ZVAl. The bromate reduction rate is GCAP > soaking Al > freeze-drying Al > soaking and heat-treating Al > pristine Al, and using GCAP just 30 min is taken to completely reduce bromate to bromide in neutral solution. Mechanism analyses revealed that Al surface treating or covered by fine γ-Al2O3 phase can promote the hydration and breakage of Al surface passive oxide layer, resulting in a fast contact of inner Al with outside ions, leading to a high reduction rate of bromate in neutral solution. XPS analyses indicated that there are no bromate or bromide ions adsorbed on Al particle surfaces, implying that there is a high direct donating efficiency of electrons from inner Al to bromate ions in solution. Furthermore, GCAP has a good reusability and >90% bromate can be reduced even it was reused up to 4 cycles.