Strategies to enhance the stability of nanoscale zero-valent iron (NZVI) in continuous BrO3− reduction

The reduction of bromate to bromide was successfully achieved by bimetallic catalysts with NZVI support in continuous-flow reactors. The stability of NZVI-supported bimetallic catalysts was enhanced by decelerating the iron corrosion and sequential rapid passivation of the iron-Cu-Pd ensembles under optimized reaction conditions. Thus >99% bromate removal can be continuously achieved for 11 h. The lifetime of the bimetallic catalyst was further enhanced and tested under different hydraulic retention time, catalyst loading, and initial bromate concentrations. At the optimized operation conditions, the catalyst showed a complete bromate reduction by 24 h and then the reactivity slowly decreased to 20% over the next 100 h. X-ray diffraction and X-ray photoelectron spectroscopy showed that the reactive NZVI support was oxidized to Fe(II) and Fe(III) along with Cu(0) oxidation to CuO, while the oxidation state of Pd did not change. Therefore, bromate reduction occurred on the surface of reactive NZVI support and Cu(0) particle, while Pd played a role as a hydrogenation catalyst that prolonged the lifetime of the bimetallic catalyst.