Strengthened Fenton degradation of phenol catalyzed by core/shell Fe–Pd@C nanocomposites derived from mechanochemically synthesized Fe-Metal organic frameworks

Abstract

We have prepared core/shell structured hollow Fe–Pd@C nanomaterials derived from Fe-metal organic frameworks which were synthesized via cheap, fast and simple mechanochemical technique. The obtained Fe–Pd@C can steadily and continuously release Fe2+ from the galvanic corrosion of Fe0 anode to trigger H2O2 decomposition into hydroxyl radicals and cause fast (10 min) and efficient (mineralization rate 95%) degradation of phenol. The presence of low level of Pd NPs in Fe–Pd@C (mass ratio of the raw material: Fe/Pd = 100:1) facilitated fast Fe3+/Fe2+ redox cycle and thus improved the catalytic performance and pH endurance of the Fe–Pd@C. After recycled four times, Fe–Pd@C remained high catalytic performance and released low level of iron ions (2.5 mg L−1), which reduced the production of iron sludge after usage. In contrast to zero-valent iron (ZVI) and commercial physically mixed Fe/C materials, the core/shell structure of Fe–Pd@C ensured efficient electron transferring from Fe0 to carbon cathode and targets, and prevented the precipitation of iron ions on Fe0 surface, avoiding the deactivation of Fe0 and termination of Fe–C internal micro-electrolysis (IME) and extending their service life. The reactive species quenching experiments and ESR characterization proved the synergistic effect of electrons and hydroxyl free radicals on degradation of phenol. The carbon-centered DMPO radical detected in reaction solution can be regarded as a proof for the strengthened oxidation ability of the combined IME and Fenton reaction.